Growth of cubic crystalline phase structure on silicon substrates and devices comprising the cubic crystalline phase structure

ABSTRACT

A method of forming a semiconductor structure includes providing a substrate comprising a first material portion and a single crystal silicon layer on the first material portion. The substrate further comprises a major front surface, a major backside surface opposing the major front surface, and a plurality of grooves positioned in the major front surface. A buffer layer is deposited in one or more of the plurality of grooves. A semiconductor material is epitaxially grown over the buffer layer and in the one or more plurality of grooves, the epitaxially grown semiconductor material comprising a hexagonal crystalline phase layer and a cubic crystalline phase structure disposed over the hexagonal crystalline phase.

DESCRIPTION OF THE DISCLOSURE Cross Reference to Related Disclosures

The present application is a divisional application of U.S. patentapplication Ser. No. 15/374,547, filed on Dec. 9, 2016, which is acontinuation-in-part of U.S. patent application Ser. No. 14/383,833,filed on Sep. 8, 2014, now U.S. Pat. No. 9,520,472, which is a 371national stage application of PCT/US2013/032613, filed Mar. 15, 2013,which claims benefit under 35 U.S.C. § 119(e) from U.S. ProvisionalApplication No. 61/642,680 filed on May 4, 2012, the disclosures of allof which applications are herein incorporated by reference in theirentireties.

GOVERNMENT INTEREST

This invention was made with U.S. Government support under Grant No.EEC-0812056 from the National Science Foundation. The U.S. Governmenthas certain rights in the invention.

FIELD OF THE DISCLOSURE

The present application is directed to a method of growing cubiccrystalline phase structure and devices made therefrom.

BACKGROUND OF THE DISCLOSURE

III-N semiconductors are promising optoelectronic materials whose directbandgap optical emission spans the ultraviolet to infrared. Despite theimpressive progress of visible light-emitting diodes (LEDs) in thenitride material system over the past two decades, two major issues arewidely recognized: 1) the green gap, and 2) efficiency droop. The greengap refers to the fact that today's InGaN LEDs emitting in the greenhave lower efficiencies than comparable devices in the blue, or to redLEDs in the AlInGaP material system. This is an issue since thesensitivity of the human eye peaks in the green. Efficiency droop is thereduction in efficiency at high drive levels, suitable for illumination.The exact origins of these effects are not fully understood, but oftenthe polarization fields in the InGaN wurtzite material system arethought to be a root cause.

GaN and alloys including AlGaN and InGaN (or GaInN) exhibit bothhexagonal (wurtzite) and cubic (e.g., zinc-blende) phases. As usedherein, the terms AlGaN, InGaN and GaInN are shorthand notations commonin the field for Al_(x)Ga_(1-x)N, In_(y)Ga_(1-y)N and Ga_(1-y)In_(y)N.For GaN and InGaN the hexagonal (h-GaN) phase is energetically preferredand with a few exceptions, all device applications including high-powertransistors, light-emitting diodes (LEDs) and laser diodes have beendeveloped with h-GaN material.

There are potential advantages to cubic (c-GaN) material and its alloys.One advantage is that the (001) direction (i.e., the direction of growthon the (001) crystal face) is not only free of spontaneous polarization,but also free of piezo-electric polarization. The bandgap of the cubicnitrides is slightly smaller than that of the wurtzite polytypes, andtherefore the band-edge emission in bulk crystals of cubic GaInN haslonger wavelength than in wurtzite crystals with the same indiumconcentration. The general absence of internal electric fields in c-GaNLEDs can eliminate the redshift associated with the quantum-confinedStark effect (QCSE).

Another potential benefit of cubic GaN is the high hole mobility, whichis reported to reach 350 cm²V⁻¹s⁻¹ in cubic GaN on GaAs. A practicaladvantage of (001) c-GaN is that it can be cleaved along the {110}planes, which are perpendicular to the (100) growth direction. Thiscould be a major advantage for device fabrication, e.g. the fabricationof laser diode devices. Further, based on theoretical calculations, ithas been suggested that the Auger-recombination in the blue-green regioncould be smaller in c-GaInN structures than in their wurtzitecounter-part. This could impact the efficiency droop effects.

According to the literature, c-GaN has been successfully grown by plasmaassisted molecular beam epitaxy (MBE) or metal organic vapor phaseepitaxy (MOVPE) on different substrates, including 3C—SiC, 6H—SiC (assuper lattice), GaAs, and Si (001). Also, growth of nano-wires withcubic GaN has been demonstrated by MBE. In the case of growth on GaAs,large free-standing samples with 100 μm thickness have been achieved.Novikov et al., “Molecular beam epitaxy as a method for the growth offreestanding zinc-blende (cubic) GaN layers and substrates,” J. Vac.Sci. Technol. B 28, vol. 28, no. 3, pp. C3B1-C3B6, October 2010.However, it took those authors around 8 days to grow such material. Itremains difficult to keep optimal growth conditions for such longdurations, and the best material quality was believed to have beenachieved only within the first 10 μm starting from the substrate. Thisthickness however would be sufficient for use in LEDs.

Novikov also recently demonstrated the feasibility of growingfreestanding cubic GaN with a thickness of more than 50 μm on a GaAssubstrate of 7.62 cm (3 inch) diameter. “Zinc-blend (cubic) GaN bulkcrystals grown by molecular beam epitaxy,” Phys. Stat. Sol. (c), vol. 8,no. 5, pp. 1439-1444, May 2011. Novikov also demonstrated cubicAl_(x)Ga_(1-x)N layers in a very wide range of alloy compositions. Whilethese are impressive results, it is generally agreed that such longgrowths are not compatible with cost-effective manufacturing of LEDs inhigh volume.

Structures with cubic GaInN/GaN multi-quantum wells (MQW) have beenreported on 3C SiC, where PL emission was observed up to a wavelength of520 nm. Simple p-GaN/n-GaN junction LEDs have been reported on GaAs. Theelectroluminescence (EL) emission at 430 nm was attributed to originatefrom impurity-related recombination and its intensity showed a lineardependence on the drive current density in the range of 50-300 A/cm². Ap-GaN/i-GaN/n-AlGaN junction LED (emission at 477 nm) as well as adouble heterojunction LED with GaInN active layer grown on GaAs(emission at 430 nm and 470 nm) have been demonstrated. It can beinferred from the published EL spectra of these devices that theintensity depends linearly on the drive current. However, the totallight output power from these devices is not known.

Recently, a GaInN/GaN LED grown by ammonia-MBE has been demonstrated. Itwas grown on freestanding cubic GaN templates by MBE on GaAs and showedEL around 460 nm. There is also published work on short wavelengthdevices. Near UV emission at 370 nm in photoluminescence (PL) from cubicAlGaN/GaN multi-quantum wells with varying width can be modeled usingsquare-well potentials, which was interpreted as absence of polarizationfields along the (001) direction.

It is fair to say that the above described techniques for growingc-group-III-N compounds have involved isolated efforts that have notbeen suitable and accepted for device fabrication. Many of the resultsshowed significant levels of defects including uncontrolled spatialvariations between c-GaN and h-GaN materials. The h-GaN material remainsthe better material, the most explored for device applications, and theonly phase used for today's commercial devices.

The epitaxial growth of high quality, c-group-III-N compounds at aphysical scale applicable to practical device fabrication is also notwell established. This is at least partially due to various problemssuch as uncontrolled phase mixtures with the hexagonal phase and someissues on the selection of substrates for epitaxy related to themismatch in crystal symmetry and lattice constant. Generally, sapphireand SiC have been employed as substrate materials but these areincompatible with the mainstream semiconductor technology thatexclusively uses Si(001) substrates. In spite of its predominant use formicroelectronics, Si has not been extensively investigated as asubstrate for c-group-III-Nitrides because of these growth problems,and, for optical applications, because of the intrinsic light absorptionin any remaining Si after the growth.

An emerging theme in modern crystal growth is the integration of theexquisitely controlled growth capabilities of MBE and MOVPE withdeveloping large-area nanoscale lithography capabilities. The usefullength scale for the lithography is less than or comparable to an adatomdiffusion length during growth. Recently, relying on large-areananoscale interferometric lithography, certain inventors of thisdisclosure demonstrated the growth of c-GaN with a controllable,symmetry-induced phase separation from the hexagonal phase during growthon a deep sub-micron scale Si(111)-faceted v-groove fabricated into aSi(001) substrate. S. C. Lee, et al., Appl. Phys. Lett. 84 (2004) 2079.This proves the availability of the epitaxial growth of c-group-III-Nmaterials on a Si(001) substrate at the nanoscale regime and is directlycompatible with current Si microelectronics technology.

Further advancements in growth of c-group-III-N materials that overcomeone or more of the deficiencies of current growth techniques, such asthose mentioned above, would be a desirable addition to the field ofIII-N semiconductors.

SUMMARY OF THE DISCLOSURE

An embodiment of the present disclosure is directed to a semiconductordevice. The semiconductor device includes a substrate comprising agroove. A buffer layer is formed on a surface of the groove. The bufferlayer comprising at least one material chosen from AlN, GaN orAl_(x)Ga_(1-x)N, where x is between 0 and 1. An epitaxially grownsemiconductor material is disposed over the buffer layer, at least aportion of the epitaxially grown semiconductor material having a cubiccrystalline phase structure.

Another embodiment of the present disclosure is directed to a method offorming a semiconductor device. The method comprises providing a planarcrystalline substrate comprising a groove exposing different crystalfaces than the planar surface. A buffer layer is deposited over thesubstrate. The buffer layer comprises at least one material chosen fromAlN, GaN or Al_(x)Ga_(1-x)N, where x is between 0 and 1. A semiconductorlayer is epitaxially grown over the buffer layer, at least a portion ofthe epitaxially grown semiconductor layer having a cubic crystallinephase structure.

Yet another embodiment of the present disclosure is directed to a methodof forming a semiconductor structure. The method comprises providing asubstrate comprising a first material portion and a single crystalsilicon layer on the first material portion. The substrate furthercomprises a major front surface, a major backside surface opposing themajor front surface, and a plurality of grooves positioned in the majorfront surface. A buffer layer is deposited in one or more of theplurality of grooves. A semiconductor material is epitaxially grown overthe buffer layer and in the one or more plurality of grooves, theepitaxially grown semiconductor material comprising a hexagonalcrystalline phase layer and a cubic crystalline phase structure disposedover the hexagonal crystalline phase.

Still another embodiment of the present disclosure is directed to alight emitting diode. The light emitting diode comprises a substratecomprising a Group III/V compound semiconductor material having a cubiccrystalline phase, an active region being positioned in the cubiccrystalline phase. A first metal contact and a second metal contact arepositioned to provide electrical connectivity to the light emittingdiode, at least one of the first and second metal contacts beingtransparent to visible light. After fabrication, the light emittingdiode is not attached to a substrate comprising a Group IV semiconductormaterial.

Another embodiment of the present disclosure is directed to anintermediate semiconductor structure. The intermediate semiconductorstructure comprises a substrate comprising a first material portion anda single crystal silicon layer positioned on the first material portion.The substrate further comprises a major front surface, a major backsidesurface opposing the major front surface, and a groove positioned in themajor front surface. A buffer layer is disposed in the groove. Anepitaxially grown semiconductor material is disposed over the bufferlayer and in the groove. The epitaxially grown semiconductor materialcomprises a hexagonal crystalline phase layer and a cubic crystallinephase structure disposed over the hexagonal crystalline phase layer.

Additional embodiments and advantages of the disclosure will be setforth in part in the description which follows, and can be learned bypractice of the disclosure. The embodiments and advantages of thedisclosure will be realized and attained by means of the elements andcombinations particularly pointed out in the appended claims.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the disclosure, as claimed.

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate several embodiments of thedisclosure and, together with the description, serve to explain theprinciples of the disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1C illustrate a method of epitaxially growing a cubiclattice semiconductor and a resulting device structure formed using themethod, according to an embodiment of the present disclosure. FIG. 1Ashows a schematic cross-sectional view of a partially made device beingmade by the process illustrated by FIGS. 1A to 1C. FIG. 1B shows aschematic cross-sectional view of a partially made device being made bythe process illustrated by FIGS. 1A to 1C. FIG. 1C shows a schematiccross-sectional view of a partially made device being made by theprocess illustrated by FIGS. 1A to 1C.

FIG. 2A shows an example of a buffer layer, according to an embodimentof the present disclosure.

FIG. 2B shows an example of a buffer layer, according to an embodimentof the present disclosure.

FIG. 3A shows growth of a buffer layer on a patterned substrate,according to embodiments of the present disclosure.

FIG. 3B shows growth of a buffer layer on a different substrate patterncompared to that of FIG. 3A, according to embodiments of the presentdisclosure.

FIG. 4 shows a result of a 30 min GaN growth, which resulted inirregular GaN growth and alloying problems.

FIGS. 5A and 5B show a thicker AlN buffer layer that reduced oreliminated the alloying problem shown in FIG. 4, according to anembodiment of the present disclosure. FIG. 5A shows a cross-section ofthe thicker buffer layer in wide grooves. FIG. 5B shows fully mergedsidewalls in a V-shaped groove.

FIG. 6A shows an example of structures grown after the optimization ofnucleation and buffer layers.

FIG. 6B shows an example of structures grown after the optimization ofnucleation and buffer layers.

FIG. 7A shows a top-view image with striations in the central part ofthe V-groove and perpendicular to the V-groove direction. FIG. 7B showsa birds-eye-view of a cross-section of a regrown sample.

FIG. 8A shows the cross-section of an exemplary individual GaN stripe(with enhanced contrast for clarity).

FIG. 8B illustrates an epitaxially grown multiple quantum well (MQW)structure, according to an embodiment of the present disclosure.

FIGS. 9A, 9B, and 9C are scanning electron microscope (SEM) images ofexample groove cross-sections. FIG. 9A shows an array of v-groovesfabricated into a Si(001) substrate.

FIG. 9B is an SEM image of the cross section of the epitaxial layersgrown on the grooves in FIG. 9A with a planar top surface. FIG. 9Creveals the surface morphology in top-down view that is slightlyroughened by surface undulation along and some bumps near the edges ofeach stripe.

FIG. 10 shows a cross section tunneling electron microscope (TEM) imageof the epilayers on a single v-groove corresponding to the dashed box inFIG. 9B.

FIG. 11A shows a scanning tunneling electron microscope (STEM) image ofthe solid box in FIG. 10 revealing example In_(x)Ga_(1-x)N/GaN MQWs.FIG. 11B is a crystal orientation map identified from the fiveIn_(x)Ga_(1-x)N layers of FIG. 11A.

FIG. 12A presents the details of change in crystal shape throughfaceting at the front growth surface as revealed in FIG. 11A.

FIG. 12B present the details of change in crystal shape through facetingat the front growth surface as revealed in FIG. 11A.

FIG. 13 presents PL spectra in the temperature range of 10-290 Kobtained from example In_(x)Ga_(1-x)N/GaN quantum wells.

FIG. 14A shows an example of neighboring GaN stripes.

FIG. 14B shows an example of neighboring GaN stripes.

FIG. 15A shows an SEM cross-section of an example LED structure.

FIG. 15B shows a schematic drawing of the LED structure of FIG. 15A.

FIG. 16A illustrates a schematic cross-section of an LED with a cubicGaN active region, according to an embodiment of the present disclosure.

FIG. 16B illustrates an assembly of the multiple stripes of FIG. 16Binto a large area LED using an interconnect layer, according to anembodiment of the present disclosure.

FIG. 17 illustrates a method of using a mask to block h-GaN growth,thereby allowing only the c-GaN to continue growing, according to anembodiment of the present disclosure.

FIG. 18 shows an exemplary cubic GaN LED device.

FIG. 19 shows a graph of data collected from several examples of thepresent disclosure.

FIG. 20A shows a graph of data collected from several examples of thepresent disclosure.

FIG. 20B shows a graph of data collected from several examples of thepresent disclosure.

FIG. 21A shows a graph of data collected from several examples of thepresent disclosure.

FIG. 21B shows a graph of data collected from several examples of thepresent disclosure.

FIG. 22 shows a region where focused ion-beam milling had been used toremove the h-GaN regions from InGaN quantum well structures, accordingto an example of the present disclosure.

FIG. 23A shows a graph of data collected from examples of the presentdisclosure.

FIG. 23B shows a graph of data collected from examples of the presentdisclosure.

FIG. 24 shows an example of a Ga—Si alloying problem that can be reducedby employing a buffer layer.

FIG. 25 illustrates a transistor, according to an embodiment of thepresent disclosure.

FIG. 26A shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 26A to 26F,according to an embodiment of the present disclosure.

FIG. 26B shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 26A to 26F,according to an embodiment of the present disclosure.

FIG. 26C shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 26A to 26F,according to an embodiment of the present disclosure.

FIG. 26D shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 26A to 26F,according to an embodiment of the present disclosure.

FIG. 26E shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 26A to 26F,according to an embodiment of the present disclosure.

FIG. 26F shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 26A to 26F,according to an embodiment of the present disclosure.

FIG. 27 illustrates a photodetector, according to an embodiment of thepresent disclosure.

FIG. 28A illustrates a laser geometry in an as-grown configuration; FIG.28B illustrates the laser geometry after removal of the semiconductorsubstrate.

FIG. 29A shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29B shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29C shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29D shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29E shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29F shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29G shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29H shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29I shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29J shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29J,according to an embodiment of the present disclosure.

FIG. 29K shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29K,according to an embodiment of the present disclosure.

FIG. 29L shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29L,according to an embodiment of the present disclosure.

FIG. 29M shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 29A to 29K, and29M according to an embodiment of the present disclosure.

FIG. 30A illustrates an example of a silicon substrate 100 having av-groove 106 formed therein.

FIG. 30B illustrates an example of a silicon substrate 100 having atruncated v-groove 106 formed therein.

FIG. 31A shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 31A to 31C,according to an embodiment of the present disclosure.

FIG. 31B shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 31A to 31C,according to an embodiment of the present disclosure.

FIG. 31C shows a schematic cross-sectional view of a partially madedevice being made by the process illustrated by FIGS. 31A to 31C,according to an embodiment of the present disclosure.

FIG. 32 shows an epitaxially grown semiconductor material bonded to ahandle substrate, according to an embodiment of the present disclosure.

FIG. 33 shows an epitaxially grown semiconductor material bonded to ahandle substrate, according to an embodiment of the present disclosure.

DESCRIPTION OF THE EMBODIMENTS

Reference will now be made in detail to various exemplary embodiments ofthe present application, examples of which are illustrated in theaccompanying drawings. Wherever possible, the same reference numberswill be used throughout the drawings to refer to the same or like parts.

An embodiment of the present disclosure is directed to a semiconductordevice 10, as illustrated in FIG. 1C. The device comprises a substrate12. The substrate comprises a groove 14 formed in crystallinesemiconductor. The sidewalls of the groove are (111) faces of thecrystalline semiconductor. A buffer layer 16 is formed in the groove 14.The buffer layer 16 comprises at least one material chosen from AlN, GaNor Al_(x)Ga_(1-x)N, where x is between 0 and 1. An epitaxially grownsemiconductor layer 18 is disposed over the buffer layer 16. A portionof the epitaxially grown layer 18 has a cubic crystalline phasestructure 18 b.

Substrate

Referring to FIG. 1A, the substrate 12 employed for manufacturing thedevices of the present disclosure can be any type of substratecomprising single crystal silicon having a (100) lattice structure. Forexample, the substrate 12 can be a free-standing silicon wafer, such asthose cut from a single crystal boule, as is well known in the art.Alternatively, the substrate can comprise other materials on which thesingle crystal silicon material is a portion thereof, such as, forexample, a silicon-on-glass substrate or a silicon epitaxial layer grownon, or bonded to, a base substrate, referred to as silicon-on-insulator.The silicon can be doped or undoped. In yet another embodiment, asubstrate comprising GaAs having a (100) lattice structure can beemployed.

The substrate 12 comprises at least one groove 14. The groove can be anyshape that provides (111)-faceted groove surfaces that are suitable forepitaxial crystal growth of the buffer layer 16. For example, a v-grooveor a flat-bottomed groove can be formed in a silicon or GaAs substrateto provide (111)-faceted sidewalls.

Referring to FIG. 1A, the width of the groove, W, can range from a fewnanometers to any width that will allow formation of the cubic latticeregion. In an embodiment, W is comparable to a diffusion length of a Gaadatom under the epitaxial growth conditions, which is generally severalmicrons, or less. In an embodiment, the width can be about 3, 5, 8 or 10microns or less. For example, W can range from about 100 nm to about5000 nm, or about 200 nm to about 500 nm. These ranges for W can applyto any of the grooves in any of the embodiments for forming cubiccrystalline material described herein.

The length of the groove can be any desired length, limited only by thesize of the available wafer. For example, the length of groove 14 can becomparable to the width of groove 14 or longer, such as a length rangingfrom about 10 or 100 times longer to about 1,000,000 times longer thanthe width of groove 14.

The groove can be formed by any suitable method that provides thedesired (111)-faceted surfaces. Examples of suitable methods includelithographic patterning and etching techniques, such as interferometriclithography followed by an anisotropic wet etch of the patterned surfaceusing, for example, KOH or related wet-etch chemistries, includingsolvent-based chemistries. A variety of other lithographic and etchingtechniques can be employed, as would be understood by one of ordinaryskill in the art.

Buffer Layer

Referring to FIG. 1B, buffer layer 16 can be epitaxially grown in groove14. In an embodiment, the buffer layer comprises an AlN nucleationlayer. An Al_(x)Ga_(1-x)N interlayer can be deposited on the nucleationlayer, where x can range from 0 to 1 (thereby encompassing AlN and GaN),for the purpose of growing cubic III-nitrides on silicon wafers. In anembodiment, x is greater than 0 and less than 1.

Buffer layer 16 plays a part in the overall success of the growthprocess. Buffer layer 16 can serve as a strain relief layer to increasethe crystal quality of the grown cubic III-nitride material.Additionally, buffer layer 16 can reduce or prevent alloying of thesubsequently formed crystal layer 18 with material from the substrate.For example, Ga—Si alloying has been shown to occur during epitaxialgrowth of GaN on silicon substrates. An example of the alloying problemis shown in FIG. 24.

The buffer layer 16 can be sufficiently thick to prevent such alloying,which can be problematic. On the other hand, if buffer layer 16 is toothick, cracking of the buffer layer is likely. In an embodiment, thethickness of the buffer layer can be in the range for example, fromsub-monolayer up to about 1 μm, such as about 1 nm to about 1 micron, orabout 5 nm or 10 nm to about 100 nm or 500 nm.

In an embodiment, the concentration of Al and Ga in the buffer layer 16is graded through at least a portion of the thickness of the bufferlayer. In an alternative embodiment, the concentration of Al and Ga inbuffer layer 16 is substantially constant through the thickness ofbuffer layer 16.

In an embodiment, the concentration of Al and Ga in the buffer layer 16and its thickness are varied separately or in combination along at leasta portion of its cross section. In an alternative embodiment, theconcentration of Al and Ga in buffer layer 16 and its thickness aresubstantially constant separately or in combination through its crosssection. In an embodiment, the composition of the buffer layer (e.g.,concentration of Al and Ga) can vary with the different crystal planesit covers. For example, the composition may be different on the bottomportion 106 c of groove 106 (FIG. 29A) than on the sidewalls 106 a or106 b.

In yet another embodiment, the concentration of Al and Ga varies in astepwise manner though at least a portion of the thickness of bufferlayer 16. For example, buffer layer 16 can comprise two or more layerswith one or more different Al_(x)Ga_(1-x)N compositions having steppedconcentrations. The concentration can be stepped in any desired manner.As an example, in one layered portion of the buffer layer x can be about0.7, and in a second layered portion of the buffer layer x can be about0.3. Another embodiment can use one or more graded buffer layers, wherex varies continuously from, for example, about 1 to 0, through thethickness of the layer. The buffer layer may or may not include anucleation layer, such as AlN, in addition to the Al_(x)Ga_(1-x)Nlayers. In yet another embodiment, an AlN layer is employed alone,without a Ga containing portion of the buffer layer.

The Al_(x)Ga_(1-x)N buffer layers can be smooth or rough. A relativelysmooth buffer layer can have a root-mean-square (RMS) surface roughnessvalue in the range from about 0.1 nm up to and including 1 nm, or more,depending on the crystal plane. In an embodiment for c-plane GaN, thesurface roughness value is generally less than 1 nm, such as about 0.2to about 0.3 nm (RMS); and would be considered relatively rough with asurface roughness value larger than 1 nm (RMS); such as a value rangingfrom 1.1 nm to about 2 nm or 20 nm (RMS). However, for non-polar andsemipolar GaN (on bulk GaN), a smooth value may range from about 1 nm toabout 2 nm (RMS).

Any other suitable buffer layer materials can be employed in theembodiments of the present disclosure in addition to or in place of theabove described buffer layer materials. Any suitable epitaxial growthmethod can be used to form the buffer layer. Suitable examples includeMBE and MOVPE. In the case of MOVPE, each MOVPE reactor system isslightly different, and therefore optimal growth conditions on Si (111)faceted sidewalls of a groove can vary. The potential parameter spacecan be large, because many combinations of temperature, pressure, gasflows, and layer compositions are possible. Selected example growth runsare described herein to provide some guidance in the selection of MOVPEgrowth conditions.

Epitaxially Grown Layer

In an embodiment, the epitaxially grown layer 18 comprises a cubicIII-nitride material. For example, the epitaxially grown layer cancomprise c-GaN and/or c-In_(y)Ga_(1-y)N, where y is greater than 0 andequal to or less than 1. Other examples of suitable cubic III-nitridematerials include GaAsSbN, InAlAsN, InGaAsN, AlGaN, BN, AlGaBN andInAlGaBN. Still other cubic III-V materials could be formed, such asGaAs, AlGaAs or InGaAs. The epitaxially grown layer 18 comprises asecond crystalline lattice structure in addition to the cubic latticestructure. In an embodiment, epitaxially grown layer 18 includes both ahexagonal lattice outer region 18 a and a cubic lattice inner region 18b.

While the theoretical basis of the formation of the cubic layer is notfully understood, experimental observations provide some suggestions asto the mechanism. What is known about this mechanism will now bedescribed with respect to a GaN (or InGaN) growth on a Si (001)substrate, although a similar mechanism may apply to other III-Nmaterials grown on (001) substrates. The initial phases of GaN (orInGaN) growth are h-GaN (or h-InGaN) that nucleates on the three-foldsymmetric Si {111} faces. As noted above, h-GaN (or h-InGaN) is thelower energy phase and forms preferentially over c-GaN (or c-InGaN). Asthis growth proceeds on the {111} sidewalls of the v-groove, opposingc-axes are formed perpendicular to the {111} sidewalls on which theyhave nucleated, such that the c-axes of the adjacent crystals lie in theSi {110} plane and are at an angle of about 105° to about 115°, or about109.5° to one another. The c-axis is the direction of the h-GaN (orh-InGaN) with a larger lattice constant than the other two orthogonalcrystal directions, e.g. the h-GaN (or h-InGaN) lattice is elongatedalong the c-axis direction. As the growth proceeds, these two h-GaNregions merge near the apex of the groove. The crystal structure cannotsupport the two c-axis directions and the symmetric growth frontstherefore provide a driving force for a phase segregation leading to theformation of the c-GaN (or c-InGaN) material in or near the center ofthe v-groove where the growth regimes overlap. This is different thangrowing GaN on planar Si(001) or a shaped surface that does not providethe desired driving force, in which you get a random phase separationthat is not useful for the purpose envisioned here. It should be notedthat while the symmetry of the epitaxial layer is the same as that ofthe Si substrate, the lattice constant of the c-GaN (or c-InGaN) isfully relaxed and is not constrained by the underlying Si latticeconstant.

FIG. 8B illustrates an epitaxially grown MQW structure formed in anepitaxially grown layer 18, according to an embodiment of the presentdisclosure. As seen from FIG. 8B, the epitaxially grown layer includesan inner region 20 of c-GaN and an outer region 22 of h-GaN. Region 24of FIG. 8B illustrates alternating layers of thicker GaN and thinnerIn_(y)Ga_(1-y)N that form quantum wells. Employing alternating layers toform quantum wells is generally well known in the art. As illustrated,these alternating layers are formed in both the cubic inner region 20and the hexagonal outer region 22.

Referring again to FIG. 1, epitaxial layer 18 can be grown by anysuitable method, such as MBE or MOVPE. The selected method can be thesame as or different than the epitaxial method used to grow the bufferlayer 16. Any suitable source materials can be employed. For example, inthe case of forming In_(y)Ga_(1-y)N, any suitable gallium, nitrogen andindium source materials can be employed. Suitable source materials foruse in MBE and MOVPE are well known in the art. One caveat is that Alcontaining materials are generally highly reactive with atmosphericoxygen. Suitable encapsulation and in-situ etching techniques can beused to protect and/or remove native and other oxides if theAl-containing layer is to be exposed to air during transfer betweengrowth modalities or on other occasions. Determining suitableencapsulation and/or in-situ etching techniques is within thecapabilities of a person of ordinary skill in the art.

The epitaxially grown layer can have any desired thickness. For example,the epitaxially grown layer 18 can have a thickness ranging from asub-monolayer to about 10 μm. The length and width dimensions of theepitaxially grown layer 18 can largely be determined by the structuringof the substrate (e.g., the length and width of the groove 14). Thelength of layer 18 may range from, for example, about 10 or 100 timeslonger to about 1,000,000 times longer than the width of groove 14. Suchstructures can be referred to as nanowires or quantum wires.

In an embodiment, a plurality of the epitaxially grown cubic layers cansimultaneously be grown in a plurality of adjacent grooves. Each of theplurality of epitaxial layers can comprise both hexagonal and cubicphase lattice structures, such as c-GaN/c-In_(y)Ga_(1-y)N regions andh-GaN/h-In_(y)Ga_(1-y)N regions. The resulting epitaxially grown layersmay or may not comprise a plurality of separated MQW cubic regions.

In an embodiment, an optional planarization step may be included afterthe epitaxial growth of any of the identified layers or the entirestructure. In this way, the application of a subsequent epitaxial growthstep or the application of a subsequent processing step may be supportedor may achieve a higher overall process yield. The planarization can beperformed by any suitable method, examples of which are well known inthe art.

In an embodiment, the separate cubic regions can subsequently beelectrically connected in parallel, series or any combination thereof.For many applications, both in electronics and in optics, it isadvantageous to connect a number of adjacent nanowires in parallel toprovide a higher current carrying capability than is available with asingle nanowire. In some electronics applications it may be desirable toprovide an alternate electrical configuration, as is common in modernintegrated circuits.

In some instances, it may be desired to reduce or prevent growth of thehexagonal crystal phase while allowing the cubic lattice to continuegrowing. In an embodiment, a blocking layer can be formed to reduce orprevent growth of the hexagonal phase portion of the epitaxial layer 18.For example, a c-GaN region and an h-GaN region can be separated by ablocking layer. An example of a technique employing a blocking layer isdiscussed below in the description of FIG. 17.

Devices

The cubic phase epitaxial layers of the present disclosure can beemployed in a variety of semiconductor devices. Examples of such devicesinclude light emitting diodes (LEDs), laser diodes, photodetectors andtransistors.

In an embodiment, a semiconductor device comprises strips of theepitaxially grown layers and silicon regions. Electronic devices can bepositioned in both the epitaxially grown layer and the silicon regions.

In an embodiment, forming the devices of the present disclosure caninvolve removing at least a portion of the substrate 12. Exampletechniques for removing the substrate are described in more detailbelow. In an embodiment, forming the devices described herein caninvolve completely or partially removing h-GaN or h-InGaN quantum wellsfrom the epitaxially grown layer.

FIG. 25 shows one example of a MOSFET transistor 30 in a cross-sectionof a cubic lattice region 18 b, formed according to methods of thepresent disclosure. The transistor can include a gate electrode 32,source and drain regions 34 and a gate dielectric 38, as is well knownin the art. Source and drain regions can be doped with n-type or p-typedopants, as can some or all of the remaining portion of cubic region 18b. Doping to form MOSFET active regions is well known in the art. Forexample, the source and drain regions 34 can be doped with an n-typedopant and the remaining portion of the cubic lattice region 18 b can bedoped with a p-type dopant, or vice versa. In an embodiment, portions ofthe MOSFET can also be formed in hexagonal lattice regions of theheterophase lattice structures described herein.

While transistor 30 is illustrated with the source-drain carriertransport under the length of gate 32 perpendicular to the lengthdirection of the cubic lattice region 18 b within the groove, thetransistor can be positioned in any desired manner with respect to thecubic lattice region 18 b. For example, the position of transistor 30can be rotated 90° so that the carrier transport under gate 32 isdirected parallel to the length of the cubic lattice region within agroove, which runs into the page in FIG. 25.

FIG. 27 illustrates one example of a photodetector that employs a cubiclattice region 18 b, formed according to methods of the presentdisclosure. The substrate 12 can be any substrate material disclosedherein, such as, for example, Si or GaAs. Similarly, the regions 18 aand 18 b can respectively be any hexagonal or cubic semiconductormaterials disclosed herein, such as a h-GaN region 18 a and a c-GaNregion 18 b. The active region 62 can be an InGaN quantum well, or anyother quantum well material disclosed herein. The regions 18 a, 18 b and62 can be doped to form heterojunction(s) so as to provide a functionalphotodetector, as is well known in the art.

Any desired technique can be used to electrically connect devices formedin the cubic lattice regions with each other and with other devices onthe substrate surface. In an embodiment, selective area decomposition ofprecursor gas is used to form electrical connections to the cubiccrystalline devices. Suitable methods for performing selective areadecomposition are well known in the art.

Stripe LEDs

To obtain the desired size of cubic lattice regions for the devices ofthe present disclosure, the widths of the groove 14 can be adjusted. Anysuitable size groove widths can be employed. For example, groove widthsof 100 nm to 10 μm were investigated, although groove widths outside ofthis range can be used. Suitable examples within this range includethose described above with respect to the width, W, in FIG. 1. It isreasonable to expect that the resulting cubic GaN regions are of similarsize as the groove widths, which would be sufficient to fabricate LEDdevices. Cubic GaN regions with μm-sized widths have been obtained usingthe methods of the present disclosure.

FIG. 16A illustrates a schematic cross-section of a proposed LED with acubic GaN active region. Individual stripes can be separated by etchingof the material between the v-grooves in any desired manner, which mayinclude etching of layers of cubic crystalline or hexagonal crystallinematerial or any other material grown between the structures. As anexample, portions of overgrown cubic crystalline material can be removedand replace with the interlevel dielectric (ILD) structures shown inFIG. 16B using any suitable photolithography, etching and depositionprocesses, examples of which are well known in the art. The top contactcan be a transparent conductive oxide or a semi-transparent metal. Thus,in an embodiment, the grown GaN layers are patterned by conventionalphotolithography and etching techniques to isolate the stripes of cubicGaN, as shown, for example, between the ILD structures of FIG. 16B. Thequantum-well active region and the p-GaN and n-GaN layers can be formedas part of a single GaN growth sequence that occurs prior to patterningof the stripes. Alternatively, the wafer with the cubic GaN can bepatterned, and then a growth mask can be used to selectively re-grow thecubic GaN active region only on the exposed cubic GaN regions.

FIG. 16B illustrates an assembly of multiple stripes of FIG. 16A into alarge area LED using an interconnect layer, according to an embodimentof the present disclosure. Metal can be deposited on the back-sideand/or front side of the wafer to provide desired contact formation.Since the silicon substrate is non-transparent, the light can beextracted through the top contact, which can be a transparent conductingoxide or a thin, semi-transparent metal or layers of other conductivematerials (e.g., graphene or graphene-like materials). Multiple stripescan be electrically connected together with an insulating interlayerdielectric (ILD) and interconnects, which can comprise any suitableconducting material, such as metal, doped polysilicon or graphene, thatonly occupy a small fraction of the final device, as illustrated in FIG.16B. In such a configuration the loss of effective light-emitting areacould be reduced.

Both geometries shown in FIGS. 16 and 17 retain the Si substrate, whichcan be an issue for LEDs because of the strong Si visible absorption. Inboth cases, it may be desirable to remove the silicon substrate. Thiscan be accomplished using any suitable technique. For example, thesample can be bonded to a new handle substrate, such as a transparent,non-transparent, or reflective substrate, with a transparent contactlayer such as ITO. The Si substrate can then be selectively removed byany suitable method. In an embodiment, the back side of the substratecan be coated to form the second contact. There are many variants onthis scheme familiar to the LED fabrication community, any of which canbe employed, as would be understood by one of ordinary skill in the art.One such example of a flip-chip bonding technique for electricalconnection to LEDs is described in more detail below. As is well knownin the art, the resulting triangular shape of the new top surface thatcan result from this technique may enhance the light extractionefficiency compared to a plane parallel geometry.

A schematic process sequence for the removal of the Si is shown in FIG.26. FIG. 26A is the as-grown c-GaN/h-GaN (18 b/18 a) on a Si substrate(12) as discussed above, including, for example, InGaN quantum wells andp-n junctions. An optional process (not shown) is to fill the spacesbetween the GaN growth and above the GaN with a dielectric material thatcould include, for example, SiO₂ (such as TEOS) or polymers such as, butnot limited to, benzocyclobutene (BCB), which is generally well known inthe art as a dielectric for use in microelectronics. This can befollowed by an etch back to expose the top surface of the GaN forcontacting. FIG. 26B shows a handle wafer (52) with two or moreadditional thin film layers (53,54) to provide electrical and mechanicalcontact to the GaN. In FIG. 26C the GaN wafer is inverted and bonded tothe handle wafer, making electrical contact to one side of the p-njunction. In FIG. 26D the Si substrate 12 is removed, using acombination of polishing and selective etching of the Si and of anydielectric layer in the case of SOI. FIG. 26E shows an optional step ofremoving the h-GaN, leaving just the c-GaN material. FIG. 26F shows twoadditional layers, a dielectric isolation layer (55) and a top contactlayer (56). This bonding scheme is well developed in many other cases,such as, for example the bonding of infrared detector arrays, fabricatedin materials such as InSb, HgCdTe or GaAs to silicon read out integratedcircuits. Such bonding is routinely carried out with many millions ofindividual contacts. The steps presented here are exemplary only.Further process details can be worked out following well known industrypractice adapted for GaN materials, as would be readily understood byone of ordinary skill in the art.

From a processing stand point, it would be ideal to have planar cubicGaN films, so that all technologies and processes for regular LEDs maybe used. To obtain these continuous films, a growth mask comprising, forexample, SiO₂, can be employed so that only the cubic phase can growfurther and these regions can then coalesce by lateral overgrowth overthe mask. The growth of these structures could include a GaN cappinglayer to clad the ends of the QWs to reduce nonradiative transitions atthe interface with amorphous materials (interlayer dielectric or air).

FIG. 17 illustrates a method of using a mask 48 to block the h-GaN,thereby allowing only the c-GaN to continue. This method is described inmore detail in U.S. Pat. No. 8,313,967, issued on Nov. 20, 2012, thedisclosure of which is hereby incorporated by reference in its entirety.Once the h-GaN is blocked the rest of the structure including the InGaNQWs can be added. Then the growth of the c-GaN can be continued tocoalescence, or a segmented device can be formed. This method can beapplied to grow layers of any of the cubic crystalline materialsdescribed herein.

Patterning conductive layers, which can comprise metal, dopedpolysilicon or any other conductive material suitable for devicefabrication, for electrically connecting the devices of the presentapplication can be performed by any suitable method. Optical lithographytools are commercially available that have the alignment and patterningcapability to form electrical contacts useful in sub micron dimensioncubic lattice regions of the present disclosure. However, suchlithography tools are currently relatively expensive, and without suchtools, the experimental realization of the proposed electricallyconnected stripe LEDs, or other device cubic lattice devices of thepresent disclosure, can prove challenging. To provide a method that canutilize less expensive tools for alignment and patterning of the cubiclattice regions, an approach was adopted that employs selective areadecomposition of a precursor gas. This method includes providing anarray of insulated pads for probing. In an embodiment, this wasaccomplished using photolithography and lift-off, as discussed ingreater detail below. However, any suitable method could be employed forproviding the desired electrical contacts.

Regions for the contact pads were defined by photoresist, andelectron-beam evaporation was used to deposit a stack of SiO₂ (200 nm),Ti (20 nm), and Au (100 nm). A fine metal (Pt) contact was depositedreaching from the contact pad to the center of an individual GaN stripeby beam induced machining (BIM). Other insulators and metals can be usedinstead of SiO₂, Ti and Au. Other metals suitable for contacts, such astungsten, can also be used instead of Pt.

BIM is usually performed by the use of a focused ion beam (FIB) tool toremove material. However, BIM can also be used to deposit new material,including conductive material, such as metal or doped polysilicon;dielectric material or semiconductive material. Selective decompositionof precursor gas is one form of BIM that can be employed, although otherforms of BIM could also be used.

During BIM, the gas can be supplied by means of a gas injection systemthat transports the gas near the region where the planned depositionwill occur. The precursor gas is decomposed by a beam of electrons orions, and leaves a residue of material determined by the precursor gasin the area where the beam has induced the decomposition. The beamdiameter, scanning rate, duration and gas flow rates determine the finalform and amount of material that gets deposited.

As an example, a precursor gas containing platinum and the electron beamof a commercially available combined SEM-FIB tool was used for theselective decomposition. This yielded an approximately 100 nm wide metalline. The thickness of this metal line was controlled by the depositiontime, and a duration of several tens of seconds yielded thicknesses onthe order of 1 μm. The result for one cubic GaN LED device is shown inFIG. 18. For this device, the part of the Pt contact 52 on the GaNstripe 54 has a length of 7.8 μm. The contact to the n-side of thestructure (not shown) was made by soldering the Si-wafer to a copperblock. Part of the probing pad 50 is visible, and the Pt metal line inthe center contacts to the p-side of the GaN stripe.

Laser Structures

In an embodiment, the stripes of the LED devices of the presentdisclosure can form one dimensional waveguide structures with only asmall number of modes. This geometry is well suited to the realizationof laser structures. The number of modes is roughly given by A/(λ/2n)²where A is the cross section of the stripe and n is the refractive indexof the GaN. The number of modes can vary depending on the device. Forthe example structure of the LED device of FIG. 18, the number of modeswas roughly about 25. A smaller v-groove would result in a significantlyreduced number of modes.

The length of the stripes can be any suitable length, limited only bythe lithographic capability and size of the substrate. Example nanowirestructures have been made that are about 1 cm, which is believed to befar longer than other known nanowire structures. Example lengths of thestripes can range from about 10 nm or less to about 50 cm, such as about1, 10 or 100 microns to about 1, 10 or 30 cm.

The material can cleave perpendicular to the stripe, providing goodmirror surfaces. Even without a good cleaved surface, the small numberof modes means that there is high reflectivity back into the propagatingmodes in the stripe.

The Si is highly absorbing to radiation at visible wavelengths, whichcan potentially be problematic for laser structures. However, asdiscussed above, there are straightforward approaches to removing theSi. Another possible problem is that the h-InGaN quantum wells to theside of the c-InGaN wells may provide a lower energy level, siphoningcarriers from the c-InGaN. This can be addressed by removing the h-GaNQW regions. FIG. 22 shows a region where focused ion-beam milling hasbeen used to remove the h-GaN regions. Alternatively the blockingtechnique of FIG. 17, discussed above, can be applied before the growthof the InGaN QWs.

Both electrical and optical pumping are appropriate for investigatinglasing possibilities. One of ordinary skill in the art would be readilyable to implement the devices described herein to fabricate lasers foreither electrical or optical pumping.

The light-output power vs. current graphs for the same cubic GaN LEDs asin FIGS. 20 and 21 are shown in FIGS. 23A and 23B, respectively. Thisdata shows that in both devices there is a current range in which thelight output power increases faster than linearly proportional to thecurrent. Specifically, for FIG. 23A this is observed in the range of 50μA to 140 μA. Specifically, for FIG. 23B this is observed in the rangeof 40 μA to 60 μA. Both those findings are indications that lightamplification by stimulated emission may be occurring. Furthermore, itis possible that by the specifics of the described structure an opticalcavity may have been formed that could act as a resonator to supportsuch stimulated emission to induce laser diode action in these devicestructures.

Examples of laser devices are illustrated by FIGS. 28A and 28B. FIG. 28Aillustrates a quantum well laser device 70 comprising a semiconductorsubstrate 12 on which a heterophase lattice region 72 is formed. Forexample, the region 72 can comprise outer h-GaN and inner c-GaN latticeregions. Any of the other group III nitrides as described herein can beemployed in place of GaN. Laser device 70 includes a quantum well region74, as is well known in the art. Quantum well region 74 can comprise asuitable group III nitride material, such as InGaN. Semiconductorregions above and below the quantum well can be doped with p-type orn-type dopants, as is well known in the art. For example, a regionimmediately below the quantum well 74 can be doped with n-type dopantsand a region immediately above quantum well 74 can be doped with p-typedopants, or vice versa. In an embodiment, multiple quantum wells can beemployed instead of a single quantum well, as is also well known in theart.

FIG. 28B illustrates another embodiment of a device 76 in which the Sisubstrate 12 has been removed and the heterophase lattice region 72 hasbeen bonded to another substrate 78. The heterophase lattice region 72can be made of the same materials and/or doped as described for thedevice of FIG. 28A. Multiple quantum wells can be formed if desired.Substrate 78 can be any suitable material, such as doped or undopedsemiconductor or insulator material. In an embodiment, the substrate 78is transparent to the radiation emitted by the quantum well laser device76.

The present disclosure teaches, among other things, growth onsub-am-sized and μm-sized V-grooves in silicon as a method for formingcubic GaN structures and cubic GaN LEDs. A contrast change in SEM isobserved between the GaN near the groove sidewalls and the material nearthe groove center. These cubic regions can have a width on the order of,for example, several hundred nanometers. For undoped and MQW structures,the cubic phase in the stripe center was confirmed by electronbackscattering diffraction (EBSD) phase identification. The top surfaceof the cubic region in the MQW structure exhibited a (001) plane.Band-edge emission and luminescence from GaInN/GaN MQWs in cubic GaNwere observed by cathodoluminescence (CL).

Additional Device Structures and Methods for Making Devices

An embodiment of the present disclosure is directed to a method offorming a semiconductor structure. In an embodiment, as shown in FIG.29A, the method comprises providing a substrate comprising a firstmaterial portion and a single crystal silicon layer on the firstmaterial portion, such as, for example, a silicon-on-insulator substrate100. Silicon-on-insulator substrate 100 comprises a major front surface102, a major backside surface 104 opposing the major front surface 102,and a plurality of grooves 106 positioned in the major front surface.The silicon-on-insulator substrate 100 comprises a single crystalsilicon device layer 100 a over a buried insulator layer 100 b, which inturn is positioned on a bulk layer 100 c. As an example, device layer100 a and bulk layer 100 c can both be single crystal silicon, andburied insulating layer 100 b can be a silicon dioxide layer.Alternatively, single crystal silicon 100 a can be on any other suitablebase substrate that provides sufficient structural support for, and etchselectivity with, the single crystal silicon layer 100 a, including basesubstrates that include a single conductive, semiconductive orinsulative material or two or more of such materials, and may or may notbe considered a silicon-on-insulator type substrate. In an embodiment,the bottom portion of the truncated v-grooves is defined by a portion ofthe buried insulator layer 100 b. One or more of the plurality ofgrooves 106 can be truncated v-grooves, each truncated v-groovecomprising a first diagonal sidewall 106 a, a second diagonal sidewall106 b opposing the first diagonal sidewall, and a bottom portion 106 cthat is parallel with the major front surface 102 of the substrate 100.The diagonal sidewalls 106 a and 106 b are {111} crystal faces of thesingle crystalline silicon 100 a.

Other suitable substrates and/or groove types can be employed in placeof the silicon-on-insulator substrate having truncated v-grooves shownin FIG. 29A. For example, either truncated v-grooves or v-grooves thatare not truncated can be formed in a silicon-on-insulator substrate thathas a device layer 100 a that is thick enough to form the groovecompletely in the device layer (e.g., the bottom surface 106 c of thegroove is silicon). FIG. 30A illustrates an example of a substrate 100having a v-groove 106 formed therein. FIG. 30B illustrates an example ofa substrate 100 having a truncated v-groove 106 formed therein. Thesubstrate 100 of FIGS. 30A and 30B can be any of the substratesdescribed herein, such as single crystal silicon substrates or singlecrystal silicon formed on a base substrate, such as SOI substrates,where the silicon in the substrate has a (001) exposed major surface forprocessing (e.g., the surface into which the grooves are formed is a(001) silicon facet).

Referring to FIG. 29A, a patterned insulating layer 108 is formed on themajor front surface of the substrate 100 by any suitable method, such asconventional deposition, photolithographic and/or etching techniques.One of ordinary skill in the art would readily be able to form thepatterned insulating layer 108. In an embodiment, the method cancomprise depositing an insulating layer on the major front surface ofthe substrate prior to depositing the buffer layer, patterning theinsulating layer to expose stripes of the substrate, and forming theplurality of grooves 106 in the exposed substrate regions. Insulatinglayer 108 may or may not be protected during etching of the grooves 106,depending on the material used for insulating layer 108 and the type ofetch chemistry employed. In an embodiment, the patterned insulatinglayer 108 comprises a material that is stable at growth temperatures ofGaN, such as about 1000° C. or more. In an embodiment, the insulatinglayer 108 can be deposited prior to formation of the grooves 106 and canact as an etch mask during formation of the grooves 106. Etching to formthe grooves 106 can be carried out using any desired etching techniquesuitable for forming a v-groove in a silicon substrate. In anembodiment, grooves 106 are anisotropically wet etched with aKOH-chemistry that selectively slows dramatically on the {111} faces.Other suitable etch chemistry can be employed. The etch can be carriedout for a sufficient length of time so as to undercut the edges ofinsulating layer 108, as shown in FIG. 29A. In this case, theover-etching of the device layer 100 a produces grooves 106 that have agreater width than the opening in the insulating layer 108.Alternatively, the etch can be carried out so that no such undercutstructures are formed, as shown in FIG. 30B.

As described above, the v-grooves etched into a Si(001) facet expose{111} sidewall facets. The grooves can have any of the groove shapesand/or dimensions as described herein. The grooves 106 can have anydesired length. For example, they can extend completely across a wafer.As another example, the length can be about 10 microns to about 1000microns or more, such as about 50 microns to about 500 microns. In anembodiment, the length of the grooves is at least 5 times the depth ofthe grooves, such as 10 to 10,000 times the depth, where the length isthe dimension of the groove into, and perpendicular to the surface of,the drawings and the depth is the greatest depth as measured between theupper major surface of device layer 100 a and the bottom portion 106 cof the grooves. Thus, the epitaxial structures grown in the grooves 106can be similar to a triangular cross section fiber. The dimensions canbe controlled to provide for single mode for propagation along thegroove. For example, the dimensions of the cross section of the fibercan be controlled to fulfill the geometric requirements for thepropagation of a specific guided optical mode, e.g. single modepropagation similar to that in many optical fibers and laser dioderesonators.

Referring to FIG. 29B, a buffer layer 112 is formed in one or more ofthe plurality of grooves 106. Any suitable buffer layer material can beemployed. As an example, buffer layer 112 can be epitaxially depositedand can be any of the buffer layers described herein. In an embodiment,as shown in FIG. 29B, the buffer layer 112 can be selectively depositedon the sidewalls 106 a and 106 b. Alternatively, buffer layer 112 can beformed over the entire surface of groove 106, including the bottom 106 cand sidewalls 106 a and 106 b.

A semiconductor material 114 is epitaxially grown in one or more of theplurality of grooves 106 over the buffer layer 112. The epitaxiallygrown semiconductor material 114 comprises a hexagonal crystalline phaselayer 116 and a cubic crystalline phase structure 118 disposed over thehexagonal crystalline phase layer 116 in one or more of the plurality ofgrooves 106.

During the epitaxially growing of semiconductor material 114, a gap 120is formed between the hexagonal crystalline phase layers 116 and thebottom portion of the truncated v-groove 106 c. In an embodiment, atleast a portion of the gap 120 is filled with a gas, such as air or anyother suitable gas. In another embodiment, at least a portion of the gap120 is filled with a buffer layer material, such as material from theformation of buffer layer 112. While the gap is depicted in the figuresas having a triangular cross-section, the gap cross-section may haveother shapes. In an embodiment, the cross-section is a triangle havingthe following dimensions: a bottom side that is the width of the bottom106 c of the groove; and sides given by the combined thickness of thebuffer layer 112 and the hexagonal crystalline phase layer 116 at thepoint of collision of the hexagonal crystalline phase layer 116 fromopposite sides of the groove, which is the point at which the cubiccrystalline phase begins. All or substantially all of the area withinthat triangle may be a void (e.g., a gas filled gap) where no materialhas grown at a sufficient rate to hinder the collision of the growthfronts from the opposing sides of the groove in the top apex of thetriangle. The void and its dimensions in respect to the width and depthof the groove reflect a design parameter for the controlled nucleationof the cubic phase GaN. While it is not necessary that gap 120 becompletely empty of material deposits, it preferably does not fill fromthe bottom up before the two sides of the hexagonal crystalline phaselayer 116 have collided

In an embodiment, the truncated grooves 106 may provide better controlof epitaxial growth compared to a complete (untruncated) groove. Asdescribed above, where the groove is truncated the hexagonal crystallinestructures that form on the {111} sidewalls grow a certain distancebefore colliding with each other. In truncated grooves withbottom-width, w, and depth of groove, d (FIG. 29A), the cubiccrystalline phase structure will first nucleate at a height, h (FIG.29B), above the groove bottom, which coincides with the point at whichthe two hexagonal crystalline phase structures meet. For example, thisheight of nucleation can be equal to

${\frac{w}{2}\tan \mspace{11mu} \phi},$

where the angle, φ=35.25°, and is defined by the underlying cubicsubstrate crystal and is equal to half the angle defined by theintersection of two {111} planes. The width, w, of the flat bottom ofthe grooves 106 may be chosen in such a way that the cubic crystallinephase structure 118 will first nucleate at a specific height withrespect to the bottom of the groove. For example, if

${w < \frac{2d}{\tan \mspace{11mu} \phi}},$

then the cubic crystalline phase structure will nucleate beneath the topsurface of the substrate as in FIG. 29B. The cubic crystalline phasewill reach the width of the opening in the insulating layer, x, at athickness,

$t = {\frac{x}{2\mspace{11mu} \tan \mspace{11mu} \phi}.}$

Further, the thickness of the insulating layer 108 can be chosen in sucha way that, in combination with the protrusion of the insulating layer108 over the groove 106, the further growth of the hexagonal crystallinematerial 116 (e.g., hexagonal GaN growth, interchangeably referred toherein as wurtzite form) is arrested by the insulating layer 108, asshown in FIG. 29B. To accomplish this, the thickness of the insulatinglayer 108 can be greater than or equal to h+t−d. In this manner, thehexagonal crystalline material can be blocked from growing beyond thetop surface of the insulating layer 108 if desired, so that the topsurface of the epitaxially grown material is dominated by cubiccrystalline phase material as compared to the hexagonal crystallinephase, as illustrated in FIG. 29B.

In an embodiment, epitaxially growing the semiconductor material alsocomprises forming at least one p-n junction and/or at least one quantumwell (similar to quantum well 74 discussed above) in the cubiccrystalline phase structure 118. In an embodiment in which the resultingsemiconductor device being formed is a light emitting diode,super-luminescent light emitting diode or laser, the epitaxially growncubic crystalline phase structure 118 and optionally the hexagonalcrystalline phase 116 semiconductor can include an n-type layer 118 a(FIG. 29D), InGaN based active region 118 b that may include, forexample, one or more quantum wells, an optional AlGaN-based blockinglayer 118 c and a p-type layer 118 d (e.g., GaN p-layer). These layerscan be grown in succession as part of the cubic crystalline phasestructure 118. The p-type GaN can then be activated by any suitablemethod, such as by rapid thermal annealing in N₂ ambient or electronbeam irradiation, as is known by the person of ordinary skill in theart. Forming the n-type layer first may be advantageous because makingthe n-type material more conductive is relatively easy compared to ap-type layer. That said, in an alternative embodiment the polarity isreversed, so that the p-type layer is formed first and the n-layer isformed last. Forming such n-type and p-type layers for carrierinjection, as well as forming quantum wells for smaller bandgap andcarrier confinement, is well known, and providing suitable activeregions for an LED or laser type device in view of the guidance providedherein would be well within the ordinary skill of the art.

A major advantage of the cubic crystalline materials, such as c-GaN, isthat the (001) face of these materials is nonpolar. Thus, the strainassociated with adding the InGaN quantum wells does not induce apolarization field that acts to separate electrons and holes in a polardevice.

The growth of the semiconductor material 114 can be stopped at anydesired time. In an embodiment, the growth of the semiconductor material114 can continue until the cubic crystalline phase structure 118 extendsover insulating layer 108, as shown in FIG. 29C. Doing so may providemore flexibility as to where the quantum wells can be positioned (e.g.,in the groove structures or in the coalesced cubic crystalline materialoutside of the grooves). In embodiments where the cubic crystallinephase growth extends over the insulating layer 108, the silicon 100 acan be retained, or removed as discussed below. In an alternativeembodiment, growth of the semiconductor material 114 can be stopped whenthe semiconductor material is flush, or substantially flush, with a topsurface of insulating layer 108, as shown, for example, in FIG. 29B.

Referring to both FIGS. 29C and 29D, a backside contact 124 can beformed over the cubic crystalline phase structure 118. The backsidecontact 124 can be patterned or not patterned. An example of a patternedcontact 124 is shown in FIG. 32. Any suitable method for forming thebackside contacts can be employed, and a variety of suitable methods arewell known in the art. In an embodiment, where the device being formedis an LED, a p-side metal is deposited and annealed after epitaxialgrowth is completed and the p-type GaN layer has been activated. Thep-side metal can provide electrical contact to the p-GaN and also mayinclude additional layers so as to act as a backside mirror. This canhelp to control the direction of light emission. Choosing suitableadditional layers to add to provide a backside mirror is within theordinary skill of the art.

As shown in FIGS. 32 and 33, the epitaxially grown semiconductormaterial can be bonded to a second substrate 126, sometimes referred toas a “handle” substrate. For example, the second substrate 126 can beattached to the backside contact 124, as shown in FIG. 32. Any of FIGS.29B to 29J and 31B to 31L can include a handle substrate attached to thebackside contact 124, such as by any suitable bonding process.Alternatively as shown in FIG. 33, in an embodiment where a backsidecontact 124 is not employed, the second substrate 126 can be attacheddirectly to the cubic crystalline phase structure 118 and optionally theinsulating layer 108, depending on whether or not the cubic crystallinephase structure 118 is grown in a continuous layer over the insulatinglayer 108, as is shown in FIG. 29C.

The handle substrate 126 can optionally be transparent if light is toexit the device through the handle substrate. If thermal issues are notimportant, the material used for the handle substrate can be, forexample, fused silica. If thermal issues are important, as they are inLEDs for lighting (as an example), the material can be sapphire ordiamond, or another high thermal conductivity material. In an example,the handle substrate 126 can have matching electrical traces that areindium soldered to the contacts 124 on the GaN, or a conductive glue canbe used. There are many other handle substrate variants that can beused, and the optimal choice depends on many factors.

The purpose of the handle substrate is to provide mechanical support forthe epitaxially grown semiconductor 114 after the Si wafer is removed.It is noted that the figures are not to scale, and the thickness of thehandle substrate 126 can be, for example, 100 times or more thicker thanthe epitaxially grown semiconductor 114 in the grooves (e.g., epitaxialgrown semiconductor can be on the order of about 1 micron; while thehandle wafer can be greater than 100 microns thick.)

The method can comprise removing at least a portion of the substrate 100and optionally the hexagonal crystalline phase layer 116. FIGS. 29E to29I show an exemplary process for removing the entiresilicon-on-insulator substrate and the hexagonal crystalline phaselayer. As shown in FIG. 29E, the bulk portion 100 c of the silicon-oninsulator substrate is thinned to a desired thickness, such as by usingmechanical and/or chemical processes. Starting thicknesses for the bulkportion 100 c can be any thickness, and as an example, may be about 200microns to 1000 microns or more, such as about 300 microns. Afterthinning, the remaining thickness of bulk portion 100 c can range, forexample, from about 5 to about 50 microns, such as about 10 to about 20microns.

Access holes 130 are then optionally formed, such as by etching, in theremaining portion of the thinned bulk portion 100 c so as to expose theburied insulating layer 100 b, as shown in FIG. 29F. An etching processis then carried out to completely remove the buried insulating layer 100b, which effectively also removes the remaining bulk layer 100 c, asshown in FIG. 29G. As an example, where the buried insulating layer 108is silicon dioxide, an HF wet etch process can be employed toselectively remove the buried oxide. Forming access holes 130 may not benecessary, but can potentially speed the removal of the buriedinsulating layer 108, since the undercut etch has to proceed only forthe distance between the access holes, rather than all the way acrossthe wafer.

Referring to FIGS. 29G and 29H, the remaining portions of the siliconlayer 100 a can then selectively be removed by a suitable etchingprocess. Any suitable etch processes that can selectively remove theremaining device layer (which is e.g., silicon) without harming theIII-V compound semiconductor material 114 can be used. For example, dryor wet etches can be employed, such as a reactive ion etch or a HNA wetetch, where the HNA is mixture of hydrofluoric acid, nitric acid, andacetic acid. Other possibilities include using XeF₂ or a F-containingplasma process. Group III-nitride materials, such as GaN, are imperviousto these etch chemistries and so should not be harmed. Removing thesilicon can allow for a reduction in light absorption at the emissionwavelengths of various devices made using this process. Thus, themethods taught herein of removing silicon or any other light absorbingsubstrate materials can provide for improved c- or h-III-N opticaldevices.

The remaining structure shown in FIG. 29H is the epitaxial growncompound semiconductor without the substrate (e.g., thesilicon-on-insulator substrate). The epitaxially grown structures can bein the form of stripes, as described herein. If desired, the removalprocess can be stopped at this point and the remaining structure can beemployed for fabricating a desired device. In one such embodiment, thehexagonal crystalline material 116 is not removed. The cubic crystallinephase structure has a length dimension, a width dimension and a heightdimension, the width dimension decreasing with the height so that thestructure is tapered. The hexagonal crystalline material is formedadjacent to the tapered structure.

Alternatively, buffer layer 112 and/or hexagonal crystalline phaselayers 116 can be removed using, for example, a reactive ion or wetetch, so that only the cubic phase portion of the epitaxially grownsemiconductor material 114 remains, as shown in FIG. 29I. An example ofan etch process that may selectively remove the hexagonal materialrelative to the cubic structure is a KOH etchant, (e.g., a photoresistdeveloper solution having a weak KOH concentration).

After the hexagonal crystalline material is removed, the cubiccrystalline phase structure 118 has a length dimension, a widthdimension and a height dimension. In the holes in the insulating layer108, the width dimension decreases with at least a portion of the heightso that the structure is tapered. Gaps 131 are formed adjacent to thetapered structure.

As discussed above, the method may optionally comprise doping thehexagonal crystalline material 116 and/or the cubic crystalline material118 with a dopant chosen from an n-type dopant and a p-type dopant. Thedoping can occur during growth of the hexagonal and cubic crystallinephase structures or subsequent to growth, such as by using an ionimplantation step or any other suitable doping technique. Examples ofsuch doping techniques are well known in the art.

In an embodiment, a filler material 132 is applied to fill gaps left byremoval of the hexagonal crystalline phase layers 116 between theinsulating layer 108 and the remaining cubic crystalline phase structure118, so as to aid in providing encapsulation and/or mechanical strength.The gaps can be adjacent the remaining tapered portion of thecrystalline phase structure 118. Filler material 132 can be any suitableinsulating material, such as dielectric material that could include, forexample, SiO₂ (such as TEOS) or polymers such as, benzocyclobutene(BCB), which is generally well known in the art as a dielectric for usein microelectronics. Still other oxide or polymer materials could alsobe used as filler. A polishing process can then be carried out toplanarize the surface and optionally remove a portion of the cubiccrystalline phase structure 118 and/or the filler material 132, as shownin FIG. 29J.

To provide electrical contact to the device being formed, such as forforming superluminescent diodes, LEDs or other optical devices, a secondcontact layer 134 is then deposited. The second contact layer 134 can becontinuous or patterned, similar to the first contact layer 124. Thefirst contact layer 124 and second contact layer 134 together providefor electrical contact with a semiconductor device comprising the cubiccrystalline phase structure. In an embodiment, one or both of the firstcontact layer 124 and second contact layer 134 are transparent. ForLEDs, transparent contacts have the advantage of allowing light to exitthe device. In an embodiment, at least second contact layer 134 istransparent. In addition or instead of second contact layer 134 beingtransparent, the contact 124 and handle substrate 126 can be transparentto allow light to exit the backside of the wafer. Any suitabletransparent contact material can be employed for contacts 124 and 134,such as indium tin oxide (“ITO”) or other transparent materials known inthe art. In an embodiment where light is to exit through the backsidecontact 124, one or more additional layers and/or the contact material134 can be chosen to act as a mirror for light generated inside thesemiconductor. This can help to control the direction of light emission.Choosing suitable additional layers and/or process steps to add toprovide a mirror is within the ordinary skill of the art. After thecontacts are formed, one or more additional layers (not shown) can bedeposited to provide improved heat transfer for removing heat from thedevice and/or to provide encapsulation, as is well known in the art.

An embodiment of the present disclosure is also directed to a lightemitting diode device. Referring to FIG. 29J, the light emitting diode138 comprises a substrate comprising a Group III/V compoundsemiconductor material having a cubic crystalline phase. One or moren-type layers, p-type layers, blocking layers and/or an active regioncomprising, for example, one or more quantum wells, are positioned inthe cubic crystalline phase. The layers and active region can bearranged as described with respect to FIG. 29D, as an example. In anembodiment, the active region of the device includes multiple quantumwells, such as the multi-quantum well (“MQW”) devices of FIGS. 8B, 11Band 15B. A first metal contact 124 and a second metal contact 134 arepositioned to provide electrical connectivity to the light emittingdiode 138. At least one of the first and second metal contacts 124, 134are transparent to visible light. The metal contacts 124 and/or 134 canoptionally be patterned, such as shown by patterned contacts 136 of FIG.29K.

In an embodiment, the light emitting diode 138 is not attached to asubstrate comprising a Group IV semiconductor material, such assubstrate 100. The cubic crystalline phase structure has a lengthdimension, a width dimension and a height dimension, the width dimensiondecreasing with the height so that the structure is tapered. In anembodiment, the hexagonal crystalline material 116 is not positionedadjacent to the tapered structure (e.g., such as where hexagonalcrystalline material 116 is removed as described herein with respect toFIGS. 29H to 29I). In an alternative embodiment, all or a portion of thehexagonal crystalline phase 116, as shown in FIG. 29H, may remain aspart of the final device 138. For example, the hexagonal crystallinephase 116 could replace filler material 132 in FIG. 29J.

An embodiment of the present disclosure is also directed to a laserdiode device 180, as illustrated in FIG. 29L. FIG. 29L shows a schematiccross-sectional view of a device that is similar to the device 138 ofFIG. 29K, where the device is configured as a laser diode as describedbelow. Laser diode device 180 comprises two mirrors 182 separated by again length to form a cavity. The cavity comprises any of the cubiccrystalline material 118 of the present disclosure, such as GaN, that isformed in stripes, as described herein. The mirrors 182 can be formed bycleaving the semiconductor material or alternatively by etching thecubic crystalline material stripe. It is advantageous for the laserdiode device 180 to design the dimensions of the GaN material so thatonly one, or at most a few, transverse modes propagating along thestripe are supported in the final structure. This assures a strongoverlap between the gain and the propagating modes. The startingmaterial for the laser can either be the individual GaN stripes of FIG.29D or the overgrown GaN regions of FIG. 29C. The removal of the Sisubstrate 100 c, the SiO₂ layer 100 b and single crystal silicon 100 a,as well as the hexagonal crystalline material 116 and buffer layer 112can follow the same process sequence as described with respect to FIGS.29E through 29I. In an embodiment, absorption loss for the laser diodedevice 180 that is due to the metal contacts may be reduced by anysuitable technique, such as growing additional material that allows themetal of the contacts to be positioned further from the active modalregion, although this may allow additional modes to propagate, therebyreducing the effective gain. Accordingly, it may be desirable to designand position the contacts to balance both the reduction in gain andabsorption loss associated therewith.

An embodiment of the present disclosure is also directed to asuperluminescent light emitting device (SLED) 181, which is similar tothe device of FIGS. 29K and 29L as described above, except that thecavity mirrors 183 are deliberately tilted to form a non-perpendicularangle relative to the longitudinal direction of the stripe of cubiccrystalline material 118, as shown for example in FIG. 29M. Theparticular tilt of the mirrors in FIG. 29M is for illustrate purposesonly and the mirrors can be tilted in any suitable manner to provide thedesired functionality of the SLED device. Further, mirrors 183 can beformed by any suitable method, such as etching the stripe of cubiccrystalline material 118. One of ordinary skill in the art would readilybe able to determine a suitable design and techniques for forming themirrors 183 given the knowledge available in the art and the presentdisclosure. The cavity comprises any of the cubic crystalline material118 of the present disclosure, such as GaN, that is formed in stripes,as described herein. It is advantageous for the SLED device to designthe dimensions of the stripe of cubic crystalline material 118 so thatonly few transverse modes propagating along the stripe are supported inthe final structure. This assures a strong overlap between the gain andthe propagating modes. The starting material for the laser can either bethe individual stripes of cubic crystalline material 118 of FIG. 29D orthe overgrown cubic crystalline material 118 regions of FIG. 29C. Ifemployed, the overgrown cubic crystalline material 118 regions of FIG.29C may be patterned to form stripes using any suitable techniques, suchas photolithographic and etching techniques that are well known in theart. The removal of the Si substrate, the SiO₂ layer and the hexagonalcrystalline material 116 can follow the same process sequence asdescribed herein with respect to FIGS. 29E through 29I. In anembodiment, absorption loss due to the metal contacts may be reduced byany suitable technique, such as growing additional material that allowsthe metal of the contacts to be further from the active modal region,although this may allow additional modes to propagate, thereby reducingthe effective gain. Accordingly, it may be desirable to design andposition the contacts to balance both the reduction in gain andabsorption loss associated therewith.

An alternative process is illustrated in FIGS. 31A to 31C. The structureshown in FIG. 31A can be formed by any suitable method described herein,such as by the process described above with reference to FIGS. 29A to29I, except that a backside contact is not formed and doped layers,quantum wells and/or p-n junctions may or may not be formed in the cubiccrystalline phase structure 118. In an embodiment, only one polarity(e.g., n-type or p-type) of cubic crystalline phase III-V material isformed at the stage of stopping the localized epitaxial growth, so thatthe cubic crystalline phase structure 118 has only a single majoritydopant type (n-type or p-type). Further, as shown in FIG. 31A, a secondsubstrate 126 is attached to the cubic crystalline phase structure 118and insulating layer 108 during the manufacturing process, as describedherein above. As an example, the second substrate 126 can be attached tothe cubic crystalline phase structure 118 prior to removal of thesubstrate 100. As shown in FIG. 31A, the substrate 100, buffer layer 112and hexagonal crystalline phase structure 116 have all been removedusing the same processes as described in connection with FIGS. 29C to29I.

Referring to FIG. 31B, insulating layer 108 is also removed. Insulatinglayer 108 can be removed by any suitable selective etch process.Optional cleaning processes can be carried out to prepare the substratefor epitaxial growth. Epitaxial growth can then be carried out using thecubic crystalline phase structures 118 as seeds. During epitaxialregrowth, the cubic crystalline phase structures 118 coalesce into acubic crystalline III/V continuous film 118′, as shown in FIG. 31C.

In an embodiment, a doped layer(s), quantum wells and/or p-n junctionsare formed in the cubic crystalline phase structure 118′ duringepitaxial growth thereof. For example, after coalescing the localizedcubic crystalline phase structures into a continuous film, then devicelayers, including n- and p-doped layers and the gain material (e.g.,quantum wells, such as InGaN quantum wells) can be formed by techniquesknown in the art.

In an embodiment, the Group III/V compound semiconductor materialemployed in the methods and devices described herein, including those ofFIGS. 29A-29M, 30A-30B, 31A-31C, and 32-33, can be any of the GroupIII/V materials disclosed herein. In an embodiment, the Group III/Vmaterial is a Group III-nitride compound semiconductor material, such asany of the Group III-nitrides mentioned in the present disclosure. As anexample, both hexagonal and cubic gallium nitride (GaN), hexagonal andcubic Indium Gallium Nitride (InGaN) or hexagonal and cubic aluminumgallium nitride (AlGaN) can be grown within the patterned grooves 106.Such growth processes are described in S. C. Lee et al., Appl. Phys.Lett. 84, 2079 (2004), the disclosure of which is incorporated herein byreference in its entirety. As an example, the epitaxially grownsemiconductor material comprises a c-GaN region and optionally a h-GaNregion, as described herein. In another example, the epitaxially grownsemiconductor material comprises c-In_(y)Ga_(1-y)N, where y is greaterthan 0 and equal to or less than 1.

An embodiment of the present disclosure is directed to an intermediateproduct semiconductor structure, as shown and described herein withrespect to FIG. 29B. The intermediate product semiconductor structurecomprises a substrate 100, which can be any of the substrates describedherein. Substrate 100 comprises a major front surface 102, a majorbackside surface 104 opposing the major front surface, and a groove 106positioned in the major front surface 102. A buffer layer 112 isdisposed in the groove 106. An epitaxially grown semiconductor material114 is disposed over the buffer layer 112 and in the groove. Theepitaxially grown semiconductor material 114 comprises a hexagonalcrystalline phase layer 116 and a cubic crystalline phase structure 118disposed over the hexagonal crystalline phase layer.

In an embodiment, groove 106 is a v-groove. In yet another embodiment,groove 106 is a truncated v-groove comprising a first diagonal sidewall106 a, a second diagonal sidewall 106 b opposing the first diagonalsidewall, and a bottom portion 106 c that is parallel with the majorfront surface 102 of the substrate 100. The dimensions of the v-groovecan be any suitable dimensions, as discussed herein. As an example, theV-groove has a width measured in a plane of the major front surface, thewidth of the v-groove being less than 10 micrometers.

In an embodiment, the substrate 100 is a silicon or silicon-on-insulatorsubstrate comprising (001) single crystal silicon, the major frontsurface 102 and the bottom portion of the groove 106 c both having a{001} crystal face, the first diagonal sidewall 106 a and the seconddiagonal sidewall 106 b both having a {111} crystal face. In analternative embodiment, the silicon-on-insulator substrate comprises a(001) single crystal silicon layer 100 a formed on an insulating layer100 b, the major front surface 102 of the substrate having a {001}crystal face, the first diagonal sidewall 106 a and the second diagonalsidewall 106 b both having a {111} crystal face, and the bottom portion106 c of the groove comprising a portion of the insulating layer 100 b.

As described herein above, the semiconductor structure further comprisesan insulating layer 108 formed on the major front surface of thesubstrate 100. Any suitable insulating layer can be employed, includingsilicon oxide, such as silicon dioxide, formed by any desired method.

In an embodiment in which a truncated v-groove 106 is employed a gap 120is formed between the hexagonal crystalline phase layers 116 and thebottom portion of the v-groove 106 c, as also described herein. The gap120 can be filled with any suitable material. For example, all or atleast a portion of the gap 120 can be filled with a gas. In yet anotherembodiment, at least a portion of the gap 120 is filled with a bufferlayer material.

EXAMPLES Example 1

A line array of v-grooves with a period of 1.8 microns was fabricatedinto a Si(001) substrate by interferometric lithography with a singlelongitudinal transverse mode, frequency-tripled, yttrium aluminum garnetlaser at a wavelength of 355-nm and anisotropic wet etching based onpotassium hydroxide. The lithographic pattern was aligned so that thev-grooves were aligned approximately along the <110> direction of the Sisurface. This led to the revealing of {111} sidewalls after KOH etching.As a substrate, boron-doped Si(001) wafers with resistivity of ˜10ohm-cm were used. An electron beam-deposited Cr film (˜200 nm) wasemployed as an etch mask. Each groove comprises two {111}-type facetsforming a v-shape valley when viewed in cross section. The groove widthwas kept at ˜0.8 microns and the corresponding depth was then ˜0.6microns.

On the v-groove-patterned substrate, a buffer comprising a thin AlN and450 nm-thick GaN layer was grown first by MOVPE. The thin AlN wasemployed to avoid any nitridation on the Si surface at the beginning ofdeposition.

Example 2

On a patterned substrate similar to that of Example 1, an additional 5stacks of a ˜3 nm-thick In_(x)Ga_(1-x)N well with a ˜20 nm-thick GaNspacer, and an ˜8 nm-thick GaN capping layer were consecutively grown onthe 450-nm-thick GaN buffer layer. All layer thicknesses, both inExample 1 and Example 2, were calibrated on a sapphire (0001) plane as areference. The total amount of deposition was sufficient to induce thephase transition to cubic phase by filling up each v-groove. At the sametime, the deposition was controlled to avoid any coalescence between theepitaxial layers grown on adjacent grooves. Thus, most of the epitaxiallayers grown on individual grooves kept the identical crystal shape evenwhen growing beyond their initial filling of their respective groove.

Example 3

Examples of different buffer layers are shown in FIG. 2. In FIG. 2B thenucleation layer is about 25% thinner than in FIG. 2A. The resultinggrowth looks similar in both cases, showing good and selectivenucleation normal to {111} planes. In the example of FIG. 2, no growthoccurred on the flat top Si (100) surfaces between the v-grooves. TheGaN on the sidewalls was smooth and continuous, but the top edges wereirregularly shaped. Voids can form where the two wings from adjacentv-grooves join.

Example 4

The effect of different substrate patterns was studied in wide grooveswith flat bottoms and sharp v grooves, as shown in FIG. 3. In FIG. 3A,illustrating grooves with relatively wide spacing between the sidewalls,the GaN was thicker than in 3B, indicating that due to the reducednucleation area, the growth rate increases. This is a well-known effectin selective area growth. The GaN thickness is 510 nm and 380 nm inFIGS. 3A and 3B, respectively.

To merge the two growth fronts from the two sidewalls, longer growthtimes can be employed. In FIG. 4 the result of a 30 min GaN growth isshown. FIG. 4 shows irregular GaN growth and alloying problem due toincreased growth time. The crystal quality was degraded and some partsof the structure show the alloying problem discussed above. A thickerAlN buffer, as shown in FIG. 5A, eliminated the alloying problem, as canbe seen in FIG. 5B.

From the above example, the following can be concluded. For successfulgrowth, the thickness of the AlN nucleation layer can be varied toprevent or reduce the alloying problem. For long growth times this alonemay not be enough and a combination of low GaN growth temperature andAlGaN interlayer can be employed. The use of the AlGaN interlayer is atrade-off between selectivity and prevention of alloying.

Example 5

An example of structures grown after the optimization of the nucleationand buffer layers is shown in FIG. 6. The structure is uniform on thescale of several mm², and the SEM images reveal that the two growthfronts in the grooves merged completely. The top surface in the centerregion is not completely smooth, but shows steps and striations. The topsurface of GaN near the sidewalls is angled away from the horizontal andit shows a slightly smoother morphology than the center region. Thev-groove depth was on the order of 0.7 μm and the GaN thickness betweenthe v-shaped contrast line and the silicon was around 0.2 μm (measuredperpendicular to the Si {111} sidewalls).

To prepare for the growth of a MQW structure, an undoped cubic GaNtemplate was grown and its quality verified. It was observed that theAlN nucleation layer and the AlGaN layers interacted during growth andsharp tips of presumably AlGaN protruded into the AlN layer. Despitethis, alloying was not a problem for this structure. This structure wassubsequently used to regrow a cyan MQW structure. The MQW comprises 7pairs of GaInN/GaN layers. The equivalent super-lattice period for onepair in a planar layer is 25.2 nm. An optical microscope image inNomarski mode and a PL image are shown in FIG. 8. It was found thatafter the regrowth some areas show very smooth surface morphology, andmost of the GaN stripes in the other areas are rough on a micrometerscale. The roughness comes from parasitic growth on the GaN stripes,which produces hillocks. Between these defects, smooth, micron-sizedregions can be found along the GaN stripes.

FIGS. 7A and 7B show SEM micrographs of the regrown cyan MQW structure.FIG. 7A shows a top-view image showing striations in the central partperpendicular to V-groove direction. These striations extended to thesloped sidewall regions. The arrows mark the total width (1.3 μm) andcentral region width (0.9 μm). FIG. 7B shows a birds-eye-view of across-section of the regrown sample. The annotations identify thedifferent regions. From FIG. 7 it is evident that the morphology of there-grown MQW conformed to the template structure. The striations on thetop surface were more pronounced and also the polycrystalline growthbetween the adjacent stripes had increased. The width of the centralregion in FIG. 7A was 0.9 μm, whereas the total width of the GaN stripewas 1.4 μm. The (tilted) cross-section view in FIG. 7B shows the uniformgrowth in several grooves. It is observed that after the MQW regrowththe GaN protruded above the silicon surface, and for the most part, thestructure above the Si surface was similar to that inside the groove.Only a slight lateral overgrowth was visible, starting from thesidewalls and extending over the region between adjacent stripes.

It was possible to observe the contrast of the MQWs in SEM micrographsdue to the combined effect of different atomic composition of GaN andGaInN layers and different fracturing of the layers during cleaving.FIG. 8A shows the cross-section of an individual GaN stripe (withenhanced contrast for clarity). As shown, a large V-shaped contrastseparated the sidewalls from the central region. Several layers can beseen near the top surface. These layers were the re-grown MQWs and theyconformed to the shape determined by the template structure. It wasevident that the MQWs grew parallel to the top surface in the centralregion and they were inclined away from the horizontal on the sidewalltop surfaces. In addition, they also grew on the (inclined) verticalsidewalls. The growth rate in this direction was strongly reduced, asevident from the drastically reduced spacing between the MQWs (see FIG.8 B)).

Example 6

FIGS. 9A, 9B, and 9C are cross-section SEM images. FIG. 9A shows anarray of v-grooves fabricated into a Si(001) substrate. FIG. 9B is anSEM image of the cross section of the epitaxial layers grown on thegrooves in FIG. 9A with a planar top surface. FIG. 9C reveals thesurface morphology in top-down view that is slightly roughened bysurface undulation along and some bumps near the edges of each stripe.The top transverse lateral dimension of each epitaxial layer extends upto ˜1.5 microns.

FIG. 10 is a TEM image corresponding to the dashed box in FIG. 9B. Theregion above the dashed line corresponds to c-GaN and c-In_(x)G_(1-x)Nlayers. The insets show high resolution TEM images of the h-GaN buffernear the interface (right) and the c-GaN in the middle of the v-grooveindicated by the arrows. The inset images confirm that h-GaN was grownat the initial stage of growth and changed to the cubic phase in themiddle of the v-groove. Some possible explanations for the phasetransformation have been proposed in our previous work. Also, the slightcontrast difference along the dashed lines that match with theintersection points of different facets at the top surface clearlyreveal the formation of different phase epitaxial layers. Thus, theregion above the dashed line in FIG. 10 corresponds to c-GaN andc-In_(x)Ga_(1-x)N.

FIG. 11A shows a STEM image of the solid box in FIG. 10 revealing theIn_(x)Ga_(1-x)N/GaN MQWs. FIG. 11B is a crystal orientation mapidentified from the five In_(x)Ga_(1-x)N layers in FIG. 11A. The fivebright lines near the top surface in FIG. 11A correspond to the fiveIn_(x)Ga_(1-x)N QW layers and play a role of markers revealing the frontgrowth surface faceting that evolves during epitaxy. As seen in FIG.11B, the top surface comprises three major facets, cubic (001) at thecenter, and hexagonal (0001) and {1101} near both edges. Thec-In_(x)Ga_(1-x)N is formed in the middle of the v-groove and laterallyextends up to 1 μm over the groove. The c-GaN facets are nonpolar andfree from the piezoelectric effects impacting the optical properties ofIII-N's. The dotted and the dashed lines represent real (below the solidline of the top surface) and imaginary (above the solid line of the topsurface) cubic/hexagonal phase boundaries and the expected growthpattern for continued growth.

FIGS. 12A and 12B present the details of the change in crystal shapethrough the faceting at the front growth surface as revealed in FIG. 11.While the crystal shape in FIGS. 10 and 11 is terminated only with threefacets; as can be seen in FIG. 11B and FIG. 12B, at least four differentfacets were involved during growth. In particular, there was anadditional {1100}facet from the hexagonal phase at both edges inaddition to the three facets already identified. Based on the profile ofthe In_(x)Ga_(1-x)N layers shown in FIG. 12, it can be noticed thatthese four facet orientations have very different growth rates and theirunequal growth rates result in a layer-to-layer and facet-to-facetthickness variation of the In_(x)Ga_(1-x)N wells, leading to the changein crystal shape. From the first GaN spacer (deposited atop the firstIn_(x)Ga_(1-x)N QW layer) to the cap layer, the nominal depositionthickness is 100 nm. Then, the actual deposition thickness on each facetmeasured from FIG. 12 is:

t ₀₀₀₁ :t ¹¹ ⁰¹ :t ₀₀₁ :t ¹¹ ⁰⁰ =˜23 nm:˜83 nm:˜107 nm:˜230 nm,  (1)

where t¹¹ ⁰⁰ is the deposition thickness from the first GaN spacer tothe third In_(x)Ga_(1-x)N QW layer (i.e., two pairs of a GaN spacer andan In_(x)Ga_(1-x)N QW) since the {1101} facet is no longer available atthe fourth In_(x)Ga_(1-x)N QW layer. In Equation (1), the thickness ofthe {0001} layer is less than the nominal deposition thickness while the{1101}, (001) and {1100} thickness are greater than the nominaldeposition thickness. Then, according to one example of the presentdisclosure and from Equation (1), the relative growth rates with respectto the growth rate of (0001) plane that depend on facet orientation canbe approximately written as:

r ¹¹ ⁰¹ :r ₀₀₁ :r ¹¹ ⁰⁰ =˜3.6:˜4.7:˜10  (2)

Here, r_(X) represents the relative growth rate of each facet normalizedby that of the h-GaN(0001). Thus, (0001) is the lowest in growth ratewhile {1100} has the highest growth rate among the given facets. The{1100}-type facet and/or plane grows very fast but ultimately disappearsfrom the growth front surface in continued epitaxy. Since the filling ofindividual grooves with h-GaN in [0001] as well as c-GaN in [001]preferentially proceeds at the initial stage of growth, it can beconjectured that the growth rate of (0001) should be considerablygreater than that of (0001) observed at the edge of each epilayer inEquation (1). That is, (0001) and (0001) are very different in growthrate under the given conditions. Then, Equation (2) is consistent withreported data where the observed growth rates vary from lowest tohighest along {1101}, {1100}, and (0001).

FIG. 12A shows magnifications of areas at the junction of (001) and{1100}. FIG. 12B reveals the disappearance of the {1100} facet near theright edge of the epilayer in FIG. 11. The arrows in each figureindicate In_(x)Ga_(1-x)N layers on individual facets.

A surface analysis shows that (0001) and (0001) are a Ga-terminated(gallided) and a N-terminated (nitrided) surface, respectively, and thegallided surface is energetically more stable than the nitrided surfacefor GaN. A more stable surface is less active in bonding adatoms fornucleation.

Regarding the cross section of the epilayer on each groove in FIG. 11Aas a 2-dimensional crystal, the epitaxy proceeds with the minimizationof total surface free energy at the given cross sectional area. Thisdrives the shape of an epilayer to the equilibrium crystal shape (ECS)for the specific growth conditions. Assuming that every facet on theepilayer has the equal accessibility to the source gases supplied intoan MOVPE reactor, and a lateral dimension less than or comparable to theadatom surface migration length, the lowest total surface free energycan be maintained at any stage of the epitaxy by contracting [expanding]the areas of higher [lower] surface energy facets (e.g., the lengths ofa facet in the cross section of FIG. 11). This coincides with adatommigration across facet boundaries. In epitaxy, the contraction of acertain facet generally occurs when it has a faster growth rate than foradjacent facets (i.e., in-migration rate >out-migration rate) and as aresult accompanies the area expansion of those neighboring facets oflower surface free energy. Then, the decreasing order of growth rate isroughly proportional to the energetic stability of the given facets andthe significantly low growth rate on (0001) in Equation (2) doesn'tcontradict the reported surface analysis. Equation (1) implies thatsurface free energy of (0001) is the lowest of the other facets involvedin the crystal shape of the epilayer. On the other hand, {1100} has thehighest free surface energy. This means the adatoms on nearby (0001) and{1101} in FIG. 11B migrate onto {1100} and some of them on {1101} alsohave nonzero out-migration rate into the adjacent (001). From FIGS. 11and 12 it can be theorized that the crystal shape may evolve through thegeneration and annihilation of various facets by adatom migration thatcan be explained with ECS. It should be emphasized that the surface freeenergy is directly related to the surface reconstruction which isaffected by growth conditions during epitaxy and the order of surfacefree energy deduced from Equation (1) is valid only under the givengrowth parameters.

As revealed by the In_(x)Ga_(1-x)N layers in FIG. 11, the top surface ofc-GaN before the deposition of the first c-In_(x)Ga_(1-x)N layer isalready flat. While some of the epilayers show noticeable fluctuation inplanarization up to the 2nd In_(x)Ga_(1-x)N deposition, most of themattain the planar surface before deposition of In_(x)Ga_(1-x)N MQWs.Thus, at least three c-In_(x)Ga_(1-x)N QW layers from the top keepplanar interface parallel to Si(001) across the cubic phase region.According to ECS based on the minimization of total surface free energy,however, r₀₀₁ greater than r¹¹ ⁰¹ in Equation (2) implies that the freesurface energy of the c-GaN (001) facet is higher than that of the h-GaN{1101} and this facet will ultimately vanish out from the front growthsurface as epitaxy proceeds further. FIG. 11 also implies theannihilation of (001) in continued epitaxy, with the dashed linesrepresenting an imaginary front growth surface that would be formed withcontinued epitaxy beyond the capping layer surface. Then, the resultingcross section would comprise a rhombus-shape c-GaN totally enclosedwithin h-GaN. This variation of cross section is very important indevice applications of c-III-N's. In order to have the maximized cubicphase top (001) surface, the growth must be controlled to stop near thepoint where the cross section of the cubic phase attains the shape of ahalf of the rhombus in cross section, as in FIG. 10.

The single v-groove epilayer shown in FIG. 10 is composed of spatiallyseparated, two phase materials exposing several different facets along asingle top surface. A theoretical calculation suggests that criticalthickness of In_(x)Ga_(1-x)N on GaN with In composition of ˜0.2 is lowerby up to 20% in hexagonal phase compared with the same constituentmaterial in the cubic phase. Generally, nucleation depends on substrateorientation in the epitaxial growth of strained heterostructures.Moreover, the cubic (001) orientation has a different misfit stress thanthe neighboring hexagonal {1101} and {1100} facets. Previously, a highertensile stress in c-GaN at the center region (˜1 GPa) than in h-GaN nearthe edge (up to 0.5 GPa) has been reported over a deep sub-μm-scalev-groove.

Then, there could be a substantial issue on the nucleation ofIn_(x)Ga_(1-x)N in FIG. 10 and the In adatom migration due to the stressfrom the multiple facets on a h-surface as well as the coexistence of h-and c-GaN at the growth surface. A rigorous approach is beyond the scopeof this work. However, FIG. 12 may provide a rough idea for the Inincorporation on a multi-faceted front growth surface. First, Equation(2) can be applied to In_(x)Ga_(1-x)N QW layers to evaluate thicknessesover different facets. In FIG. 12(b), the ratio of the thickness on{1101} to the thickness on {1100} for In_(x)Ga_(1-x)N is not noticeablydifferent from that for GaN. That is, h-In_(x)Ga_(1-x)N QWs on {1100}are ˜ twice wider than that on {1100} in thickness. Then, there seems tobe the mass transport of In adatoms across the facet boundary that isalmost identical to that of Ga adatoms. If the adatom migrationconjectured from Equation (2) is applied to the c-In_(x)Ga_(1-x)N QWs on(001), they are expected to be a little thicker than those on {1101}.But, this is not confirmed in FIG. 12A. On the contrary, they lookedthinner than those of on {1101} with lower contrast. This is opposite tothe tendency observed in GaN spacers between (001) and {1101} wheregrowth on (001) catches up that on {1101} as a result of the fastergrowth rate, as discussed earlier. It is not clear whether theseobservations are due to the stress near the junction of the two facetsor some instrumental byproduct from the STEM image capture. Furtherstudy is required to understand the In incorporation onto cubic phase(001) plane bounded by hexagonal {1101} and its correlation with stressresulting from lattice mismatch and spatial phase separation.Nonetheless, it is evident that the migration and nucleation of Inadatoms are affected by the presence of the phase and facet boundariesat the growth front surface in In_(x)Ga_(1-x)N growth and as a resultthis impacts the optical and electrical properties of thec-In_(x)Ga_(1-x)N/GaN MQWs.

Example 7: Photo- and Electro-Luminescence

FIG. 13 presents the PL spectra in the temperature range of 10-290 Kobtained from In_(x)Ga_(1-x)N/GaN quantum wells of the presentdisclosure, such as those in FIG. 12. At 290 K, a single broad peak isobserved at a wavelength of 491.9 nm. This peak follows thetemperature-dependent bandgap of GaN and shifts to 478.6 nm at 10 K.Another narrow peak at 510.1 nm is evident below 60 K. The narrow peakis strengthened and becomes comparable to the broad peak in intensity at10 K. The investigation of the origin of the narrow peak is presentlyunderway. Assuming that both peaks are from the MQWs, the range of Incomposition can be roughly estimated as 0.2-0.3 in the consideration ofboth hexagonal and cubic phase. As discussed earlier, STEM reveals thepossibility that the spatial inhomogeneity of the In atoms within eachQW layer and c-In_(x)Ga_(1-x)N/GaN MQW could have the peak separationfrom h-MQWs that is less than the bandgap difference between c- andh-In_(x)Ga_(1-x)N, as a result of both thickness and concentrationvariations, and this may impact the peak splitting and the linewidthbroadening.

Example 8: LED Structures

After these encouraging results on the MQW growth, full LED structuresthat include a final Mg-doped layer (200 nm thick) were grown. For thisstructure a substrate with small V-grooves was used. The depth of theinitial grooves was 0.3 μm and the width at the top was 0.45 μm. FromFIG. 14 it can be seen that after the growth, some portions of theneighboring GaN stripes touched each other. There was a significantdensity of hillocks on the GaN stripes. Between these defects continuousstripes with lengths in the tens of micrometers were found (FIG. 14A).FIG. 14A shows a strong contrast difference between the central regionand the sidewalls. The stripes showed the familiar striationsperpendicular to the groove direction, just like those observed inundoped GaN and the MQW structures. It was particularly interesting tofind that the basic growth scheme continued even once the GaN had grownsignificantly out of the initial V-groove (FIG. 14B). The individualstripes showed some variation in height, and therefore even if mergingof the cubic GaN regions of neighboring stripes were possible (forexample using growth masks or etching), the height difference would makeit difficult to achieve consistent crystal quality.

From the SEM cross-sections (FIG. 15A), the Mg-doped layer on top of theLED structures was clearly visible with its brighter contrast. This isalso commonly observed in wurtzite LEDs on sapphire. A schematic of thestructure is shown in FIG. 15B. The introduction of the Mg dopant didnot change the growth properties significantly. There was littleMg-doped GaN on the sidewalls (facing adjacent grooves) since the GaNstripes almost touched each other before this layer was grown, andtherefore little material could enter the gap between two adjacentstripes.

Example 9: Electrical and Optical Characteristics of Cubic GaN LEDs

The IV characteristics of two cubic GaN LEDs, which were made accordingto the methods of the present disclosure and that were similar to thedevice illustrated in FIG. 18, are shown in FIG. 19. These two LEDdevices were labeled as M7 and O8 in FIG. 19. The data for these deviceshows clear diode behavior with moderate leakage. The rectifying ratioof current in forward to current in reverse direction is as high as 4.8at ±15V for the device labeled M7. Given the dimensions of the smallp-side contacts, which have an area less than 1 μm², the calculatedcurrent density is on the order of tens of kA/cm². This would be anexceptionally high current density, and it is believed that not allcurrent is flowing through this small contact, but instead is leakingthrough the contact pad. This is possible because the surface morphologyis very rough and has sharp features, which can facilitate dielectricbreakdown in the insulating layer. Additionally it was observed that theprobing needle may slightly damage the contact pad, which could also addto parasitic leakage.

Relatively strong electroluminescence (EL) was observed for the twodevices M7 and O8. The spectra data for the two cubic GaN LED devices M7and O8 are shown in FIG. 20 and FIG. 21, respectively. In particular,FIG. 20 shows spectra of device M7 in FIG. 20A (linear) and FIG. 20B(semi-logarithmic) plots. FIG. 21 shows spectra of device M7 in 21A(linear) and 21B (semi-logarithmic plots).

The EL for other devices (not shown) showed parasitic bluish emissionfrom directly under the probing needle or the corners of the probingpad. The parasitic emission was often flickering, whereas the emissionfrom the region with intentionally fabricated contacts was stable. Toquantify the emission characteristics, the light from the devices wascollected by an optical fiber (400 μm silica core) positioned a few mmabove the LED. The spectral sensitivity of the setup was calibratedindirectly using an intermediate light source. This resulted in smallartifacts in the recorded spectra in the form of shoulders on the mainpeak. It must be noted that the absolute power calibration using thisapproach has a potential large error and therefore has to be regarded asan order-of-magnitude estimate.

The wavelength of the main peak in FIG. 20A is at 489 nm at a current of140 μA, indicating that wavelength-stable electroluminescence at 489 nmwas achieved. There was negligible wavelength shift as the current wasdecreased, which is evident from FIG. 20B. At 140 μA, there are twopeaks in the red spectral region, one at 597 nm and one at 614 nm. Thereis also very little shift in the position of these two peaks over themeasured current range.

Similar results are obtained for the second device shown in FIG. 21. Themain peak at 100 μA is at 487 nm, and there is no shift in the rangefrom 20-100 μA. The strongest peaks in the red spectral region are at586 nm and 600 nm (at 100 μA). The 600 nm peak shows no shift in thecurrent range from 40-100 μA.

In conventional wurtzite GaN LEDs with the cyan or green emission, achange in current by one order of magnitude can result in peak shifts of10 nm or more due to a reduced QCSE. Therefore, the observed absence ofsuch peak shifts is a strong indication of EL from the cubic GaN region.Even when the (non-radiative) leakage through other parts of the contactpad is taken into account, this result is valid if it is assumed thatthe ratio of leakage current to current through the region of intereststays constant. Within the calibration limitations outlined above, thetotal power of device O8 at 100 μA was determined to be 6 nW with an EQEof 3×10⁻⁵.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that can vary depending upon thedesired properties sought to be obtained by the present disclosure. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

It is noted that, as used in this specification and the appended claims,the singular forms “a,” “an,” and “the,” include plural referents unlessexpressly and unequivocally limited to one referent. Thus, for example,reference to “an acid” includes two or more different acids. As usedherein, the term “include” and its grammatical variants are intended tobe non-limiting, such that recitation of items in a list is not to theexclusion of other like items that can be substituted or added to thelisted items.

While particular embodiments have been described, alternatives,modifications, variations, improvements, and substantial equivalentsthat are or can be presently unforeseen can arise to applicants orothers skilled in the art. Accordingly, the appended claims as filed andas they can be amended are intended to embrace all such alternatives,modifications variations, improvements, and substantial equivalents.

What is claimed is:
 1. A light emitting diode comprising: a substratecomprising a Group III/V compound semiconductor material having a cubiccrystalline phase, an active region being positioned in the cubiccrystalline phase; a first metal contact and a second metal contact, thefirst and second metal contacts being positioned to provide electricalconnectivity to the light emitting diode, at least one of the first andsecond metal contacts being transparent to visible light; wherein thelight emitting diode is not attached to a substrate comprising a GroupIV semiconductor material.
 2. The light emitting diode of claim 1,wherein the cubic crystalline phase structure has a length dimension, awidth dimension and a height dimension, the width dimension decreasingwith the height so that the structure is tapered, the hexagonalcrystalline material being formed adjacent to the tapered structure. 3.The light emitting diode of claim 2, wherein the cubic crystalline phaseis positioned between a first hexagonal crystalline phase and a secondhexagonal crystalline phase.
 4. The light emitting diode of claim 2,wherein the Group III/V compound semiconductor material is a GroupIII-nitride.
 5. The light emitting diode of claim 2, wherein the activeregion comprises one or more quantum wells.
 6. An intermediatesemiconductor structure comprising: a substrate comprising a firstmaterial portion and a single crystal silicon layer positioned on thefirst material portion, the substrate further comprising a major frontsurface, a major backside surface opposing the major front surface, anda groove positioned in the major front surface; a buffer layer disposedin the groove; an epitaxially grown semiconductor material disposed overthe buffer layer and in the groove, the epitaxially grown semiconductormaterial comprising a hexagonal crystalline phase layer and a cubiccrystalline phase structure disposed over the hexagonal crystallinephase layer.
 7. The semiconductor structure of claim 6, wherein thegroove is a v-groove.
 8. The semiconductor structure of claim 6, whereinthe groove is a truncated v-groove comprising a first diagonal sidewall,a second diagonal sidewall opposing the first diagonal sidewall, and abottom portion that is parallel with the major front surface of thesubstrate surface.
 9. The semiconductor structure of claim 8, furthercomprising an insulating layer formed on the major front surface of thesubstrate.
 10. The semiconductor structure of claim 8, furthercomprising a gap between the hexagonal crystalline phase layers and thebottom portion of the v-groove.
 11. The semiconductor structure of claim10, wherein at least a portion of the gap is filled with a gas.
 12. Thesemiconductor structure of claim 10, wherein at least a portion of thegap is filled with a buffer layer material.